WO2007113977A1 - Light oil compositions - Google Patents

Light oil compositions Download PDF

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Publication number
WO2007113977A1
WO2007113977A1 PCT/JP2007/054455 JP2007054455W WO2007113977A1 WO 2007113977 A1 WO2007113977 A1 WO 2007113977A1 JP 2007054455 W JP2007054455 W JP 2007054455W WO 2007113977 A1 WO2007113977 A1 WO 2007113977A1
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WO
WIPO (PCT)
Prior art keywords
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light oil
oil composition
paraffin
fuel
Prior art date
Application number
PCT/JP2007/054455
Other languages
French (fr)
Japanese (ja)
Inventor
Yasutoshi Iguchi
Hideaki Sugano
Osamu Tamura
Original Assignee
Nippon Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006097347A external-priority patent/JP4815251B2/en
Priority claimed from JP2006097515A external-priority patent/JP4914629B2/en
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to EP07737969A priority Critical patent/EP2011851A4/en
Priority to KR1020087026681A priority patent/KR101280850B1/en
Priority to US12/293,310 priority patent/US8080068B2/en
Priority to CN2007800110512A priority patent/CN101410494B/en
Priority to AU2007232025A priority patent/AU2007232025B2/en
Publication of WO2007113977A1 publication Critical patent/WO2007113977A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition

Definitions

  • the present invention relates to a light oil composition.
  • hydrorefining treatment or hydrodesulfurization treatment has been applied to straight-run gas oil obtained from a crude oil atmospheric distillation apparatus, straight-run kerosene obtained from crude oil atmospheric distillation, or the like.
  • additives such as a cetane number improver and a detergent are blended with these light oil bases as necessary.
  • Patent Document 1 describes that diesel particulate emissions can be reduced by a compression ignition engine fuel in which the content of sulfur and aromatic compounds and the ratio of isoparaffin to normal paraffin satisfy specific conditions. .
  • Patent Document 1 Japanese Translation of Special Publication 2005-529213
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a light oil composition that is excellent in ignitability and low-temperature fluidity and that can be suitably used in winter or cold regions. The purpose is to provide. Another object of the present invention is to provide a light oil composition having improved ignitability and low-temperature fluidity while sufficiently maintaining the essential quality as a diesel fuel.
  • the present inventors first analyzed the composition of light oil using a gas chromatograph 'time-of-flight mass spectrometer (hereinafter abbreviated as "GC-TOFMS"), The effect of the composition on ignitability and low-temperature fluidity was investigated. As a result, the paraffin composition in the specific carbon number range satisfies the specific conditions, and the gradual cooling cloud point and the pour point satisfy the specific conditions, respectively. As a result, the present invention has been completed.
  • GC-TOFMS gas chromatograph 'time-of-flight mass spectrometer
  • the composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-1), the slow cooling cloud point is 6.0 ° C. or less, and
  • a gas oil composition having a pour point of 7.5 ° C. or less (hereinafter referred to as “first gas oil composition” t, for convenience) is provided.
  • n represents the carbon number of paraffin
  • f (n) represents the following formula (2):
  • n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
  • the paraffin composition parameter f (n) obtained based on the ratio of normal paraffin having the same carbon number, one-branched isoparaffin, and two or more branch-isoparaffins. And the total amount of f (n) in the C10-24 range (middle side of the above formula (1-1)) is in the range of 34.0 to 40.0, and the slow cooling cloud point is 6.
  • (bZa) and (cZa) in formula (2) that is, the molar ratio of 1-branched isoparaffin and 2 or more-branched isoparaffin to normal paraffin at each carbon number is determined using GC-TOFMS as described above. Obtainable.
  • GC-TOFMS the sample components are first separated by gas chromatography, and each separated component is ionized. Next, based on the fact that the ion velocity is different depending on the mass of the flying velocity force S ions when a constant acceleration voltage is applied to the ions, the ions are mass separated, and a mass spectrum is obtained based on the difference in arrival time to the ion detector.
  • the FI ionization method is preferable because it can suppress the generation of fragment ions and can further improve the measurement accuracy of the norafine composition.
  • the measurement apparatus and measurement conditions in the present invention are shown below.
  • Carrier gas He, 1.4 mLZ min (constant flow)
  • Oven temperature Hold at 50 ° C for 5 minutes, heat up at 5 ° CZ, and hold at 320 ° C for 6 minutes
  • Measurement mass range 35-500.
  • the total strength of one-paraffin and the strength of isoparaffins with two or more branches are compared to the total strength of normal paraffin.
  • the molar ratio may be obtained directly from the mass spectrum, but based on the mass spectrum data, a graph showing the correlation between the retention time and the intensity of gas chromatography for each component having the same carbon number.
  • the peak area ratio of each component in the graph may be a molar ratio.
  • FIG. 1 is a graph showing an example of the correlation between retention time and intensity of gas chromatography of components having the same carbon number.
  • the peaks in regions A, B, and C correspond to normal paraffin, one-branch isoparaffin, and two or more branch isoparaffins, respectively.
  • the molar ratio (bZa) of the one-branched isoparaffin to the normal paraffin defined in the present invention is the ratio of the peak area S of the region B to the peak area S of the region A (bZa)
  • the molar ratio of in (cZa) is the ratio of the peak area S of region C to the peak area S of region A
  • the first light oil composition is a paraffin based on a molar ratio of one-branch isoparaffin and two-branch or more isoparaffins to normal paraffin as an index of light oil ignitability and low-temperature fluidity.
  • the composition parameter f (n) is suitable, and is first made based on the knowledge of the present inventors that GC-TOFMS is useful as a method for obtaining f (n). It can be said that the effect is extremely unexpected.
  • the cetane number is 65 or more, and the sulfur content is It is preferable that the content is 10 mass ppm or less, the aromatic content is 1 mass% or less, the naphthene content is 5 mass% or less, and the clogging point is 5 ° C. or less.
  • the composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-2), and the distillation amount E250 at a distillation temperature of 250 ° C is 5 to 45.
  • a light oil composition (hereinafter referred to as “second light oil composition” for the sake of convenience) having a slow clouding point of more than 6.0 ° C.
  • n represents the carbon number of paraffin
  • f (n) represents the following formula (2):
  • n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
  • the paraffin composition parameter f (n) obtained based on the ratio of normal paraffin having the same carbon number, one-branched isoparaffin, and two-branch or higher isoparaffin is used as an index, and the carbon number of 10 to
  • the total amount of f (n) in 24 (the middle side of the above formula (1-1)) is within the range of 37.0 to 43.0, and the E250 and the slow cooling cloud point satisfy the above conditions.
  • E250 in the present invention means JIS K 2254 “Petroleum product distillation test method
  • the distillation curve force obtained by the “pressure method” means the distillation volume at a distillation temperature of 250 ° C.
  • the cetane number is 65 or more
  • the sulfur content is 10 mass ppm or less
  • the aromatic content is 1 mass% or less
  • the naphthene content is The content of is preferably 5% by mass or less
  • the clogging point is preferably 5 ° C. or less.
  • a light oil composition that is excellent in ignitability and low-temperature fluidity and can be suitably used in winter or in cold regions.
  • a light oil composition having improved ignitability and low-temperature fluidity while sufficiently maintaining the essential quality as a diesel fuel is provided.
  • FIG. 1 is a graph showing an example of the correlation between the retention time and intensity of a gas chromatograph of components having the same carbon number, obtained using GC-TOFMS.
  • FIG. 2 is a graph showing an operation mode (relationship between time and vehicle speed) in a fuel consumption test.
  • the light oil composition according to the first embodiment of the present invention comprises the following conditions (A-l), ⁇ 1) and
  • composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-1).
  • n represents the carbon number of paraffin
  • f (n) represents the following formula (2):
  • the sum of f (n) in the range of 10 to 24 carbon atoms is 34.0 to 400. 0, preferably 360.0 to 390.0, more preferably 370.0 to 390.0, and still more preferably 375.0 to 388.0. If the sum of f (n) in the range of carbon numbers from 10 to 24 is less than 340.0, the calorific value of the capacity will be low and the fuel consumption per capacity will be greatly reduced. Viscosity will increase and proper jetting control will not be possible.
  • the aromatic content in the light oil composition according to the first embodiment is not particularly limited, but is preferably 15 volumes based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. % Or less, more preferably 10% by volume or less, still more preferably 5% by volume or less, and particularly preferably 1% by volume or less.
  • “Aromatic content” as used in the present invention refers to JPI-5S-49 97 “Hydrocarbon type test method high-performance liquid chromatographic method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content measured according to the standard.
  • the content of the naphthene in the light oil composition according to the first embodiment is not particularly limited, but is preferably 50% by volume based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. Below, more preferably 30% by volume or less, still more preferably 15% by volume or less, and particularly preferably 10% by volume or less.
  • the “aromatic content” as used in the present invention refers to the mass percentage (mass of naphthene) measured according to ASTM D2425 “Standard Test Method for Hydrocarbon Types in Middel Distillates by Mass Spectrometry”. %).
  • the sulfur content of the light oil composition according to the first embodiment is based on the total amount of the composition because the purification performance of the exhaust gas aftertreatment device of a diesel vehicle can be satisfactorily maintained.
  • the amount is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, more preferably 3 ppm by mass or less, and particularly preferably 1 ppm by mass or less.
  • the “sulfur content” in the present invention means a value measured according to JIS K 2541 “Sulfur content test method”.
  • the slow-cooling cloud point of the light oil composition according to the first embodiment is 6.0 ° C or less, preferably 7.0 ° C or less, as described above. More preferably, it is 7.5 ° C or less, and further preferably 8.0 ° C or less. If the slow-cooling cloud point is 7.0 ° C or lower, the wax can be easily dissolved even if it adheres to the filter of the fuel injection device of a diesel vehicle.
  • the “slow cooling cloud point” in the present invention means a value measured as follows.
  • the sample put the sample in a sample container whose bottom is an aluminum surface so that the thickness is 1.5 mm, and irradiate light from a height of 3 mm from the bottom of the container.
  • the “cloud point” means a cloud point measured in accordance with J IS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
  • the cloud point of the light oil composition according to the first embodiment is not particularly limited, but is preferably 0.0 ° C or less, more preferably 2.0 ° C or less, and even more preferably 5.0 ° C or less. Particularly preferably, it is 8.0 ° C or lower. If the cloud point is 0 ° C or less, even if wax adheres to the filter of the fuel injection device of a diesel vehicle, the wax tends to be easily dissolved.
  • the pour point of the light oil composition according to the first embodiment is ⁇ 7.5 ° C. or lower as described above, preferably ⁇ 10 ° C. or lower, and more preferably. Is ⁇ 15 ° C. or lower, more preferably ⁇ 20 ° C. or lower.
  • the “pour point” in the present invention means a pour point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
  • the base material constituting the light oil composition according to the first embodiment is not particularly limited as long as the light oil composition satisfies the above conditions (A-1), (B-1), (C1), One of petroleum gas oil base, petroleum oil kerosene base, synthetic light oil base and synthetic kerosene base alone, or Two or more types can be used in combination.
  • each base material does not need to satisfy the above conditions (A-1), (B-1), (C1) alone.
  • the composition may satisfy the above conditions (A-1), (B-1), and (C-1).
  • Specific examples of the petroleum-based light oil base used in the present invention include straight-run gas oil obtained from a crude oil atmospheric distillation apparatus; straight-run heavy oil obtained from an atmospheric distillation apparatus and residual Vacuum gas oil obtained by subjecting koji oil to vacuum distillation equipment; hydrorefined gas oil obtained by hydrorefining straight-run gas oil or vacuum gas oil; straight-run gas oil or vacuum gas oil under normal conditions.
  • Hydrodesulfurized diesel oil obtained by hydrodesulfurization in stages or multistages; hydrocracked diesel oil obtained by hydrocracking the above various diesel oil bases, and the like.
  • the petroleum-based kerosene base material specifically, for example, straight-run kerosene obtained from a crude oil atmospheric distillation apparatus; straight-run heavy oil or residual oil obtained from an atmospheric distillation apparatus is decompressed. Depressurized kerosene obtained by distillation equipment; hydrorefined kerosene obtained by hydrorefining straight-run kerosene or depressurized kerosene; straight-run kerosene or depressurized kerosene in one stage or multiple stages under conditions severer than ordinary hydrorefining And hydrodesulfurized kerosene obtained by hydrocracking the above-mentioned various kerosene base materials.
  • the hydrogen partial pressure during hydrodesulfurization is particularly preferably 5 MPa or more, more preferably 3 MPa or more, more preferably IMPa or more.
  • the upper limit of the hydrogen partial pressure is not particularly limited, but is preferably lOMPa or less from the viewpoint of pressure resistance of the reactor.
  • the reaction temperature during hydrodesulfurization is preferably 300 ° C or higher, more preferably 320 ° C or higher, and particularly preferably 340 ° C or higher.
  • the upper limit of the reaction temperature is not particularly limited, but is preferably 400 ° C. or lower from the viewpoint of heat resistance of the reactor.
  • the liquid hourly space velocity during hydrodesulfurization, 6h _1 less preferred instrument 4h "1 or less and more preferably tool 2h _ 1 or less is particularly preferred. Further, the lower limit of the liquid hourly space velocity is not particularly restricted From the viewpoint of drift, 0.1 lh _1 or more is preferable, and the catalyst used in the hydrodesulfurization is not particularly limited, but Ni, Co, Mo, W, Pd, Pt, etc. Examples include using two or three kinds of metals in combination. Co-Mo-based, Ni-Mo-based, Ni-Co-Mo-based, and Ni-W-based catalysts can be preferably used. From the viewpoint of versatility, Co-Mo-based and Ni-Mo-based catalysts can be used. Is more preferable.
  • the "synthetic light oil base material” is a light oil base material obtained by chemically synthesizing natural gas, asphalt content, coal, etc. as raw materials. Chemical synthesis methods include indirect liquefaction method and direct liquid solution method, and the typical synthesis method is Fischer's Tropsch synthesis method. It is not limited by. Synthetic light oil bases are generally composed of saturated hydrocarbons, and more specifically, normal paraffins, isoparaffins, and naphthenes. That is, a synthetic light oil base generally contains almost no aromatic content. Therefore, when reducing the aromatic content of the light oil composition, it is preferable to use a synthetic light oil base.
  • the "synthetic kerosene base” is a kerosene base obtained by chemically synthesizing natural gas, asphalt, coal, and the like as raw materials. Chemical synthesis methods include indirect liquefaction method and direct liquid solution method, and the typical synthesis method is Fischer's Tropsch synthesis method.
  • the synthetic kerosene base material used in the present invention is a production method of these. It is not limited by. Synthetic kerosene bases are generally composed of saturated hydrocarbons, and more specifically, normal paraffins, isoparaffins, and naphthenes. That is, the synthetic kerosene base material generally contains almost no aromatic content. Therefore, it is preferable to use a synthetic kerosene base material to reduce the aromatic content of the light oil composition.
  • the light oil composition according to the first embodiment may contain one or more of the above petroleum-based substrates and Z or synthetic-based substrates, and among them, the sulfur content It is preferable to contain a synthetic light oil base material and a Z or synthetic kerosene base material as essential components from the viewpoint of reducing the frequency of increasing the environmental load, and aromatic components.
  • the total content of the synthetic light oil base and the Z or synthetic kerosene base is preferably 20% by volume or more, more preferably 30% by volume or more, based on the total amount of the composition. More preferably, it is more preferably 40% by volume or more, and particularly preferably 50% by volume or more.
  • the light oil composition according to the first embodiment comprises the above light oil base material and Z or kerosene base material.
  • a low temperature fluidity improver include ethylene unsaturated ester copolymers typified by ethylene-vinyl acetate copolymers, alkenyl succinic acid amides, polyethylene glycol dibehenate esters, and the like.
  • Low-temperature fluidity improver such as a strong comb-like polymer such as an alkyl fumarate or an alkyl fumarate unsaturated alkyl ester copolymer, an acid such as phthalic acid, succinic acid, ethylene diammine tetraacetic acid, utlyloacetic acid
  • a strong comb-like polymer such as an alkyl fumarate or an alkyl fumarate unsaturated alkyl ester copolymer
  • an acid such as phthalic acid, succinic acid, ethylene diammine tetraacetic acid, utlyloacetic acid
  • Examples include reaction products of anhydrides and hydrocarbyl-substituted amines, and other low-temperature fluidity improvers containing polar nitrogen compounds. Use one or more of these compounds in combination. May be.
  • an ethylene vinyl acetate copolymer additive and a low-temperature fluidity improver containing a polar nitrogen compound can be preferably used to prevent wax crystal refinement and prevent coagulation sedimentation of wax. Therefore, it is more preferable to use a low temperature fluidity improver containing a polar nitrogen compound.
  • the content of the low-temperature fluidity improver is preferably 50 to 500 mg ZL, more preferably 100 to 300 mg ZL, based on the total amount of the composition. If the content of the low temperature fluidity improver is less than the lower limit, the effect of improving the low temperature fluidity due to the additive tends to be insufficient. Further, even if the content of the low temperature fluidity improver exceeds the above upper limit, there is a tendency that a further improvement effect of the low temperature fluidity commensurate with the content cannot be obtained.
  • the light oil composition according to the first embodiment may further contain a lubricity improver.
  • a lubricity improver one or more of lubricity improvers such as ester, carboxylic acid, alcohol, phenol, and amine can be used.
  • ester-based or carboxylic acid-based lubricity improver it is preferable to use an ester-based or carboxylic acid-based lubricity improver.
  • ester-based lubricity improvers are preferred.
  • a carboxylic acid-based lubricity improver is preferable from the viewpoint that the addition amount of the property improver can be reduced.
  • ester-based lubricity improvers include glycerin carboxylic acid esters and the like. Specifically, linoleic acid, oleic acid, salicylic acid, normitic acid, Examples thereof include glycerin esters such as myristic acid and hexadecenoic acid, and one or more of these can be used as appropriate.
  • the content of the lubricity improver is preferably 25 to 500 mg / L, more preferably 25 to 300 mgZL, still more preferably 25 to 200 mgZL, based on the total amount of the composition.
  • the content of the lubricity improver is less than the lower limit, the effect of improving the lubricity due to the addition tends to be insufficient. Further, even if the content of the lubricity improver exceeds the above upper limit, there is a tendency that a further improvement effect of low temperature fluidity commensurate with the content cannot be obtained.
  • the light oil composition according to the first embodiment may further contain additives other than the low-temperature fluidity improver or the lubricity improver.
  • additives include detergents such as alkenyl succinic acid derivatives, carboxylic acid amine salts, phenolic and amine-based acid detergents, metal deactivators such as salicylidene derivatives, and polydaricol.
  • Anti-icing agents such as ether, corrosion inhibitors such as aliphatic amines, alkenyl succinates, anti-static agents such as anionic, force thione, and amphoteric surfactants, coloring agents such as azo dyes, silicones, etc.
  • An antifoaming agent can be mentioned.
  • Addition amount can be, for example, 0.5% by mass or less, and preferably 0.2% by mass or less, with respect to the light oil composition. .
  • the total amount of the additive added means the added amount as an effective component of the additive!
  • the light oil composition according to the first embodiment is shown below from the viewpoint of further improving various performances. It is preferable to satisfy the conditions.
  • the cetane index of the light oil composition according to the first embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 73 or more, and particularly preferably 75 or more. .
  • the cetane number of the light oil composition according to the first embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 73 or more, and particularly preferably 75 or more. is there.
  • cetane index and cetane number refer to JIS K 2280 "petroleum oil fuel oil octane number and cetane number test method and cetane index calculation method", respectively. Means a value measured in compliance.
  • the clogging point of the light oil composition according to the first embodiment is preferably 5 ° C or less, more preferably 6 because it can suppress the clogging of the filter provided in the fuel injection device of the diesel vehicle. ° C or lower, more preferably 7 ° C or lower, particularly preferably 8 ° C or lower.
  • the “clogging point” in the present invention means a value measured in accordance with JIS K 2288 “Petroleum products—light oil clogging point test method”.
  • the kinematic viscosity at 30 ° C of the gas oil composition according to the first embodiment preferably 1. 7m m 2 Zs or more, more preferably 2. 0 mm 2 Zs or more, more preferably 2. 3 mm 2 Zs or more, preferably in JP 2. 5 mm 2 Zs or more, and preferably 5. 0 mm 2 Zs, more rather preferably is 4. 7 mm 2 Zs less, more preferably 4. 5 mm 2 Zs less, particularly Preferably it is 4.3 mm 2 Zs or less.
  • kinematic viscosity at 30 ° C means a value measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
  • the flash point of the light oil composition according to the first embodiment is preferably 45 ° C or higher, more preferably 50 ° C or higher, and still more preferably 53 °, from the viewpoint of safety during handling. C or higher, particularly preferably 55 ° C or higher.
  • the “flash point” in the present invention means a value measured in accordance with JIS K 2265 “Flame point test method for crude oil and petroleum products”.
  • the initial boiling point (hereinafter abbreviated as "IB P") is preferably 140 ° C or higher, more preferably 145 ° C or higher. More preferably, it is 150 ° C or higher, particularly preferably 155 ° C or higher, preferably 195 ° C or lower, more preferably 190 ° C or lower, further preferably 185 ° C or lower, particularly preferably 180. It is below ° C. If I BP is less than the lower limit, some light fractions are vaporized, and the amount of unburned hydrocarbons in the exhaust gas increases as the spray range becomes wider within the diesel engine.
  • the 10% distillation temperature (hereinafter abbreviated as "T10") of the light oil composition according to the first embodiment is preferably 165 ° C or higher, more preferably 170 ° C or higher, and still more preferably. 175 ° C or higher, particularly preferably 180 ° C or higher, preferably 205 ° C or lower, more preferably 200 ° C or lower, still more preferably 195 ° C or lower, particularly preferably 190 ° C or lower. is there.
  • T10 is less than the lower limit, some light fractions are vaporized, and the amount of hydrocarbons in the exhaust gas increases as the spray range becomes wider in the diesel engine. As a result, startability at high temperatures and engine rotation stability at idling tend to be reduced.
  • T10 exceeds the upper limit, the startability and drivability at low temperatures in a diesel vehicle tend to deteriorate.
  • the 50% distillation temperature (hereinafter abbreviated as "T50”) of the light oil composition according to the first embodiment is preferably 200 ° C or higher, more preferably 205 ° C or higher, and still more preferably. 210 ° C or higher, particularly preferably 215 ° C or higher, preferably 260 ° C or lower, more preferably 255 ° C or lower, still more preferably 250 ° C or lower, particularly preferably 245 ° C or lower. is there. If T50 is less than the lower limit, the fuel consumption rate, engine output, startability at high temperatures, and stability of engine rotation at idling tend to decrease in diesel vehicles. On the other hand, when T50 exceeds the above upper limit value, particulate matter (hereinafter referred to as PM! That emits engine power tends to increase in diesel vehicles.
  • PM particulate matter
  • the 90% distillation temperature (hereinafter abbreviated as "T90") of the light oil composition according to the first embodiment is preferably 265 ° C or higher, more preferably 270 ° C or higher, and still more preferably. 275 ° C or higher, particularly preferably 280 ° C or higher, preferably 335 ° C or lower, more preferably 330 ° C or lower, further preferably 325 ° C or lower, particularly preferably 320 ° C or lower. is there.
  • T90 is less than the lower limit, the fuel consumption rate, startability at high temperatures, and stability of engine rotation at idling tend to decrease in diesel vehicles.
  • the light oil composition contains a low temperature fluidity improver
  • the effect of improving the clogging point and the like by the low temperature fluidity improver tends to decrease.
  • T90 exceeds the upper limit
  • the PM discharged from the engine power tends to increase compared to the diesel motor.
  • the end point (hereinafter abbreviated as "EP") of the light oil composition according to the first embodiment is preferably 310 ° C or higher, more preferably 315 ° C or higher, further preferably 320 ° C or higher, particularly preferably 325 ° C or higher, preferably 355 ° C or lower, more preferably 350 ° C or lower, still more preferable. It is preferably 345 ° C or less, particularly preferably 340 ° C or less. If EP is less than the lower limit, the fuel consumption rate, startability at high temperatures, and engine rotation stability at idling tend to decrease in diesel vehicles.
  • the improvement effect such as clogging point due to the low temperature fluidity improver tends to decrease.
  • EP exceeds the upper limit PM emitted from engine power in diesel vehicles tends to increase.
  • the WS1.4 value of the HFRR is preferably 500 or less, more preferably 460 or less, and even more preferably 420 or less. Is less than 400.
  • the “HFRR WS1.4 value” in the present invention is an index for determining the lubricity of diesel oil. JPI-5S-50-98 “Diesel Oil” issued by the Japan Petroleum Institute It means the value measured according to the “Lubricity Test Method”.
  • the light oil composition according to the second embodiment of the present invention is characterized by satisfying the following conditions (A-2), ⁇ 2), and (ji-2).
  • composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-2).
  • n represents the carbon number of paraffin
  • f (n) represents the following formula (2):
  • n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
  • the sum of f (n) in the range of 10 to 24 carbon atoms is 37.0 to 430. 0, preferably 375.0 to 410.0, more preferably 380.0 to 40.0, and still more preferably 383.0 to 390.0. If the sum of f (n) in the range of carbon numbers from 10 to 24 is less than 370.0, the calorific value of the capacity will be low and the fuel consumption per capacity will be greatly reduced. Viscosity will increase and proper jetting control will not be possible.
  • the content of the aromatic component in the light oil composition according to the second embodiment is not particularly limited, but preferably 15 volumes based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. % Or less, more preferably 10% by volume or less, still more preferably 5% by volume or less, and particularly preferably 1% by volume or less.
  • the naphthene content in the light oil composition according to the second embodiment is not particularly limited, but is preferably 30% by volume based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. Below, more preferably 20% by volume or less, still more preferably 15% by volume or less, and particularly preferably 10% by volume or less.
  • the sulfur content of the light oil composition according to the second embodiment is preferably based on the total amount of the composition because the purification performance of the exhaust gas aftertreatment device of a diesel vehicle can be maintained satisfactorily. Is 10 mass ppm or less, more preferably 5 mass ppm or less, more preferably 3 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • E250 of the light oil composition according to the second embodiment needs to be 5 to 45% as described above, and preferably 10 to 43%. Preferably it is 15-40%, More preferably, it is 17-38%. Diesel cars with E250 below 5% The resistance of the rubber member used for the is insufficient. If the E250 exceeds 45%, the fuel consumption rate, engine output, startability at high temperatures, and engine rotation stability during idling cannot be maintained.
  • the slow cooling cloud point of the light oil composition according to the second embodiment needs to exceed 6.0 ° C as described above, and preferably 5.5. It is at least ° C, more preferably at least 5.2 ° C, and even more preferably at least 5.0 ° C.
  • the “slow cooling cloud point” in the present invention means a value measured as follows. In other words, put a sample in a sample container whose bottom is an aluminum surface so that the thickness is 1.5 mm, and irradiate light from a height of 3 mm from the bottom of the container.
  • the base material constituting the light oil composition according to the second embodiment is not particularly limited as long as the light oil composition satisfies the above conditions (A-2), (B-2), and (C-2).
  • one of petroleum-based light oil base, petroleum-based kerosene base, synthetic light-oil base and synthetic kerosene base can be used alone or in combination of two or more.
  • the light oil composition only needs to satisfy the above conditions (A-2), (B-2), and (C-2).
  • the petroleum-based light oil base material, petroleum-based kerosene base material, synthetic-based light oil base material, and synthetic-based kerosene base material used in the second embodiment are the same as those in the first embodiment, so here A duplicate description is omitted.
  • the light oil composition according to the second embodiment may contain one or more of the above-mentioned petroleum-based substrates and Z or synthetic-based substrates, and among them, the sulfur content It is preferable to contain a synthetic light oil base material and a Z or synthetic kerosene base material as essential components from the viewpoint of reducing the frequency of increasing the environmental load, and aromatic components.
  • the total content of the synthetic light oil base and the Z or synthetic kerosene base is preferably 20% by volume or more, more preferably 30% by volume or more, based on the total amount of the composition. 40% or more by volume More preferably, it is particularly preferably 50% by volume or more.
  • the light oil composition according to the second embodiment may be composed of only the light oil base and the Z or kerosene base, but may contain a low-temperature fluidity improver as necessary. it can.
  • the low temperature fluidity improver the same low temperature fluidity improver as exemplified in the description of the first embodiment can be used.
  • One low temperature fluidity improver may be used alone, or two or more low temperature fluidity improvers may be used in combination.
  • an ethylene-vinyl acetate copolymer additive and a low-temperature fluidity improver containing a polar nitrogen compound can be preferably used to promote wax crystal refinement and The use of a low-temperature fluidity improver containing a polar nitrogen compound is more preferred in terms of preventing wax aggregation and sedimentation.
  • the content of the low-temperature fluidity improver is preferably 50 to 500 mg ZL, more preferably 100 to 300 mg ZL, based on the total amount of the composition. If the content of the low temperature fluidity improver is less than the lower limit, the effect of improving the low temperature fluidity due to the additive tends to be insufficient. Further, even if the content of the low temperature fluidity improver exceeds the above upper limit, there is a tendency that a further improvement effect of the low temperature fluidity commensurate with the content cannot be obtained.
  • the light oil composition according to the second embodiment may further contain a lubricity improver.
  • a lubricity improver one or more of the ester-based, carboxylic acid-based, alcohol-based, phenol-based, and amine-based lubricity improvers exemplified in the description of the first embodiment above should be used. Can do.
  • Carboxylic acid type lubricity improvers are preferred from the viewpoint that the amount of the improver added can be reduced.
  • the content of the lubricity improver is preferably 25 to 500 mg / L, more preferably 25 to 300 mgZL, still more preferably 25 to 200 mgZL, based on the total amount of the composition.
  • the content of the lubricity improver is less than the lower limit, the effect of improving the lubricity due to the addition tends to be insufficient. Also, even if the content of the lubricity improver exceeds the upper limit, A further improvement effect of low-temperature fluidity commensurate with the amount tends to be obtained.
  • the light oil composition according to the second embodiment may further contain an additive other than the low-temperature fluidity improver or the lubricity improver.
  • additives include detergents such as alkenyl succinic acid derivatives, carboxylic acid amine salts, phenolic and amine-based acid detergents, metal deactivators such as salicylidene derivatives, and polydaricol.
  • Anti-icing agents such as ether, corrosion inhibitors such as aliphatic amines, alkenyl succinates, anti-static agents such as anionic, force thione, and amphoteric surfactants, coloring agents such as azo dyes, silicones, etc.
  • An antifoaming agent can be mentioned.
  • Addition amount can be, for example, 0.5% by mass or less, and preferably 0.2% by mass or less, with respect to the light oil composition. .
  • the total amount of the additive added means the added amount as an effective component of the additive!
  • the light oil composition according to the second embodiment is shown below from the viewpoint of further improving various performances. It is preferable to satisfy the conditions.
  • the cetane index of the light oil composition according to the second embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 75 or more, and particularly preferably 80 or more. .
  • the cetane number of the light oil composition according to the second embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 75 or more, and particularly preferably 80 or more. is there.
  • the pour point of the light oil composition according to the second embodiment is preferably 2.5 ° C or less, more preferably 5.0 ° C or less. By setting the pour point below the above upper limit, sufficient fluidity in the fuel line of diesel vehicles can be secured.
  • the clogging point of the light oil composition according to the second embodiment is preferably 1 ° C or less, more preferably 2 because it can suppress the clogging of the filter provided in the fuel injection device of the diesel vehicle. ° C or lower, more preferably 3 ° C or lower, particularly preferably 4 ° C or lower.
  • the kinematic viscosity at 30 ° C of the light oil composition according to the second embodiment is preferably 2. Om m 2 Zs or more, more preferably 2.2 mm 2 Zs or more, and further preferably 2.4 mm 2. Zs above, preferably especially 2 is a 5 mm 2 Zs or more, and preferably 4. 2 mm 2 Zs less, more rather preferably is 4.
  • mm 2 Zs less 0 mm 2 Zs less, more preferably 3. 9 mm 2 Zs less, particularly Preferably it is 3.8 mm 2 Zs or less. If the kinematic viscosity at 30 ° C is less than the above lower limit value, start-up failure is likely to occur when the diesel vehicle is used at a relatively high temperature, and engine rotation during idling is unstable. Tends to hesitate. On the other hand, when the kinematic viscosity at 30 ° C exceeds the upper limit, the amount of black smoke in the exhaust gas tends to increase.
  • the flash point of the light oil composition according to the second embodiment is preferably 60 ° C or higher, more preferably 65 ° C or higher, and still more preferably 70 °, from the viewpoint of safety during handling. C or higher, particularly preferably 75 ° C or higher.
  • the initial boiling point (IBP) is preferably 155 ° C or higher, more preferably 160 ° C or higher, and further preferably 165 ° C or higher. In particular, it is 170 ° C or higher, preferably 225 ° C or lower, more preferably 220 ° C or lower, further preferably 215 ° C or lower, particularly preferably 210 ° C or lower. If the IBP is less than the lower limit, a part of the light fraction is vaporized, and the amount of unburned hydrocarbons in the exhaust gas increases as the spray range becomes wider in the diesel engine.
  • the 10% distillation temperature (T10) of the light oil composition according to the second embodiment is preferably 175 ° C or higher, more preferably 180 ° C or higher, still more preferably 185 ° C or higher, particularly preferably. Is 190 ° C or higher, preferably 270 ° C or lower, more preferably 265 ° C or lower, still more preferably 260 ° C or lower, particularly preferably 255 ° C or lower. If T10 is less than the lower limit, some light fractions are vaporized, and the amount of hydrocarbons in the exhaust gas increases as the spray range becomes wider in the diesel engine. As a result, startability at high temperatures and engine rotation stability at idling tend to be reduced. On the other hand, if T10 exceeds the upper limit, the startability at low temperatures in diesel vehicles and And drivability tends to decrease.
  • the 50% distillation temperature (T50) of the light oil composition according to the second embodiment is preferably 230 ° C or higher, more preferably 235 ° C or higher, still more preferably 240 ° C or higher, particularly preferably. Is 245 ° C or higher, preferably 300 ° C or lower, more preferably 295 ° C or lower, still more preferably 290 ° C or lower, particularly preferably 285 ° C or lower.
  • T50 is less than the lower limit, the fuel consumption rate, engine output, startability at high temperatures, and engine rotation stability at idling tend to be reduced in diesel vehicles.
  • T50 exceeds the upper limit, particulate matter (PM) discharged from the engine power of diesel vehicles tends to increase.
  • the 90% distillation temperature (T90) of the light oil composition according to the second embodiment is preferably 285 ° C or higher, more preferably 290 ° C or higher, still more preferably 295 ° C or higher, particularly preferably. Is not lower than 300 ° C, preferably not higher than 335 ° C, more preferably not higher than 330 ° C, still more preferably not higher than 325 ° C, particularly preferably not higher than 320 ° C. If T90 is less than the lower limit, the fuel consumption rate, startability at high temperatures, and engine rotation stability at idling tend to decrease in diesel vehicles.
  • the improvement effect such as clogging point by the low temperature fluidity improver tends to decrease.
  • T90 exceeds the upper limit, the PM emitted by the engine in a diesel vehicle tends to increase.
  • the end point (EP) of the light oil composition according to the second embodiment is preferably 305 ° C or higher, more preferably 310 ° C or higher, still more preferably 315 ° C or higher, and particularly preferably 320 ° C. Further, it is preferably 355 ° C or lower, more preferably 350 ° C or lower, further preferably 345 ° C or lower, and particularly preferably 340 ° C or lower. If EP is less than the lower limit, the fuel consumption rate, startability at high temperatures, and stability of engine rotation at idling tend to decrease in diesel vehicles. Further, when the light oil composition contains a low temperature fluidity improver, the improvement effect such as a clogging point due to the low temperature fluidity improver tends to decrease. On the other hand, when EP exceeds the upper limit, PM discharged from the engine power of diesel vehicles tends to increase.
  • WS 1.4 value of HFRR Is preferably 500 or less, more preferably 460 or less, still more preferably 420 or less, and particularly preferably 400 or less.
  • the WS1.4 value satisfies the above conditions, sufficient lubricity can be secured in the injection pump of a diesel vehicle.
  • Examples 1-2 and Comparative Examples 1-3 light oil compositions having the compositions and properties shown in Table 1 were prepared.
  • Each of the light oil compositions of Examples 1 and 2 is a fuel obtained by obtaining a natural gas power wax and a middle distillate by a Fischer's mouth push reaction and subjecting them to hydrogenation treatment.
  • the diesel oil composition of Comparative Example 1 is a crude oil-derived fuel produced by general hydrorefining.
  • the light oil composition of Comparative Example 2 is a fuel obtained by obtaining a wax and middle distillate from natural gas by the Fischer's Tropsch reaction and hydrotreating it.
  • the light oil composition of Examples 1 and 2 This is a fuel with a lower degree of hydrotreatment!
  • the diesel oil composition of Comparative Example 3 is a fuel in which crude oil-derived fuel produced by general hydrorefining is further hydrotreated to further reduce sulfur and aroma.
  • Exhaust gas aftertreatment device oxidation catalyst.
  • the fuel system of the diesel vehicle was flushed with the evaluation fuel (each diesel oil composition) at room temperature.
  • the specified amount of fuel to be evaluated (1Z2 of the fuel tank capacity of the test vehicle) was applied to the fuel tank. Then, rapidly cool the ambient temperature from room temperature to 5 ° C, hold it at 5 ° C for 1 hour, slowly cool it down to ⁇ 10 ° C at a cooling rate of l ° CZh, and keep it at ⁇ 10 ° C for 1 hour.
  • the running test was started. Measurement was not possible if the 10-second cranking did not start after repeated twice at 30-second intervals.
  • Fuel injection pump row type
  • PM reduction device designated by Tokyo (Category 4 compliant)
  • Fuel used in PM reduction equipment Low sulfur gas oil (sulfur content 50 mass ppm or less).
  • Exhaust gas aftertreatment device oxidation catalyst.
  • the driving test consisted of “engine start”, “5 minutes idling”, “acceleration to 50 kmZh” and “running for 1 hour at 50 kmZh”, and the pass / fail was judged by the operating condition of the winding. Specifically, it was judged as good (S) when the vehicle was able to maintain 50kmZh over the previous run without any problems in engine start, idling and acceleration. In the first cranking, minor problems may have occurred, such as when the engine is strong enough to start but also when the vehicle's speed has dropped temporarily and then recovered. (A).
  • Fuel consumption was measured using a vehicle equipped with a diesel engine shown below.
  • the test mode is performed in the transient operation mode that simulates the actual driving shown in Fig. 2, and the fuel consumption is corrected by comparing the fuel volume flow rate consumed during the test mode with the fuel temperature and replaced with the weight value. Each result was relatively compared and quantified, with the result when the fuel was tested as 100.
  • Exhaust gas aftertreatment device oxidation catalyst.
  • Examples 3 to 4 and Comparative Examples 4 to 6 light oil compositions having the compositions and properties shown in Table 2 were prepared.
  • Each of the light oil compositions of Examples 3 to 4 is a fuel obtained by obtaining a natural gas power wax and a middle distillate by a Fischer's mouth push reaction and subjecting them to a hydrotreatment.
  • the diesel oil composition of Comparative Example 4 is a crude oil-derived fuel produced by general hydrorefining.
  • the gas oil composition of Comparative Example 5 was obtained by obtaining wax and middle distillate from natural gas by Fischer's Tropsch reaction and subjecting it to hydrogenation treatment. This is a fuel with a reduced degree of hydrotreatment compared to the light oil compositions of Examples 3-4.
  • the diesel oil composition of Comparative Example 6 is a fuel in which crude oil-derived fuel produced by general hydrorefining is further hydrotreated to further reduce sulfur and aroma.
  • Exhaust gas aftertreatment device oxidation catalyst.
  • the fuel system of the diesel vehicle was flushed with the evaluation fuel (each light oil composition) at room temperature.
  • the specified amount of fuel to be evaluated (1Z2 of the fuel tank capacity of the test vehicle) was applied to the fuel tank.
  • the ambient temperature was rapidly cooled from room temperature to 10 ° C, held at 10 ° C for 1 hour, slowly cooled to 0 ° C at a cooling rate of l ° CZh, and kept at 0 ° C for 1 hour.
  • a running test was started. Measurement was not possible if the 10-second cranking did not start after repeated twice at 30-second intervals.
  • a high temperature startability test was carried out according to the following procedure on a chassis dynamometer capable of controlling environmental temperature and humidity using the following diesel engine equipped vehicle.
  • the vehicle was refueled with 15 L of the test fuel, and then the engine was started and held by idling.
  • the ambient temperature was set to 25 ° C to stabilize the test room temperature, and the engine was stopped when the fuel injection pump outlet temperature of the idling vehicle was stabilized.
  • the engine was restarted and when the engine started normally, the environmental temperature was raised in the order of 30 ° C and 35 ° C, and the above test operation was repeated.
  • the case where the engine was started normally was regarded as acceptable (A)
  • the case where it was not activated was regarded as unacceptable (B).
  • Table 2 shows the results obtained.
  • Fuel injection pump High pressure distribution type
  • Exhaust gas aftertreatment device oxidation catalyst.
  • a soaking test was conducted according to the following procedure.
  • One of the compounds that make up rubber is acrylonitrile, which has a combined acrylonitrile mass center value of 25% or more and 35% or less of the total.
  • the test fuel was heated to 100 ° C and held in accordance with the test, and the test rubber member was immersed in it for 70 hours.
  • the volume change of the test rubber member after 70 hours was measured to evaluate the resistance of the rubber member. Table 2 shows the results obtained.
  • Fuel consumption was measured using a vehicle equipped with a diesel engine shown below.
  • the test mode is performed in the transient operation mode that simulates the actual driving shown in Fig. 2, and the fuel efficiency is the value obtained by correcting the fuel volume flow consumed during the test mode with the fuel temperature and replacing it with the weight value.
  • Each result was relatively compared and quantified, with the result when the fuel was tested as 100. Table 2 shows the results obtained.
  • Exhaust gas aftertreatment device oxidation catalyst.

Abstract

A light oil composition in which C10-24 paraffins have a composition satisfying the following formula (1-1) and which has a cloud point in gradual cooling of -6.0°C or lower and a pour point of -7.5°C or lower; and a light oil composition in which C10-24 paraffins have a composition satisfying the following formula (1-2) and the distillate amount E250 measured at a distillation temperature of 250°C is 5-45% and which has a cloud point in gradual cooling above -6.0°C. In the formulae (1-1) and (1-2), n is the number of carbon atoms in each paraffin and f(n) indicates that compositional parameter for a Cn paraffin which is represented by the formula (2). In the formula (2), n is an integer of 10-24, and a, b, and c indicate the proportions (in terms of molar proportion) of the Cn n-paraffin, Cn isoparaffin having one branch, and Cn isoparaffin having two or more branches, respectively, in all Cn paraffins.

Description

明 細 書  Specification
軽油組成物  Light oil composition
技術分野  Technical field
[0001] 本発明は、軽油組成物に関する。  [0001] The present invention relates to a light oil composition.
背景技術  Background art
[0002] 従来、軽油の基材としては、原油の常圧蒸留装置から得られる直留軽油、原油の 常圧蒸留により得られる直留灯油などに、水素化精製処理や水素化脱硫処理を施し たものが知られている。また、これらの軽油基材には、必要に応じてセタン価向上剤、 清浄剤などの添加剤が配合される。  Conventionally, as a base material for light oil, hydrorefining treatment or hydrodesulfurization treatment has been applied to straight-run gas oil obtained from a crude oil atmospheric distillation apparatus, straight-run kerosene obtained from crude oil atmospheric distillation, or the like. Is known. In addition, additives such as a cetane number improver and a detergent are blended with these light oil bases as necessary.
[0003] ところで、近時、大気環境の改善及び環境負荷の低減の観点から、ディーゼルェン ジン排出ガスのクリーンィ匕が求められている。そこで、力かる要求に応えるベぐディ ーゼル排出ガス中の汚染物質を低減できる軽油基材の開発が進められている。例え ば、下記特許文献 1には、硫黄及び芳香族化合物の含有量並びにイソパラフィンとノ ルマルパラフィンとの比が特定条件を満たす圧縮着火エンジン燃料によってディー ゼル粒状排出物を低減できることが記載されている。  [0003] Recently, from the viewpoint of improving the air environment and reducing the environmental burden, there is a demand for cleanliness of diesel engine exhaust gas. In light of this, development of a light oil base material that can reduce pollutants in the exhaust gas of the veggie that meets the strong demands is underway. For example, Patent Document 1 below describes that diesel particulate emissions can be reduced by a compression ignition engine fuel in which the content of sulfur and aromatic compounds and the ratio of isoparaffin to normal paraffin satisfy specific conditions. .
特許文献 1:特表 2005 - 529213号公報  Patent Document 1: Japanese Translation of Special Publication 2005-529213
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] し力しながら、上記従来の軽油であっても、実用上十分な特性を有しているとはい えない。 [0004] However, even the above-described conventional light oil does not have practically sufficient characteristics.
[0005] 例えば、燃費性能の点においては、特に、冬季又は寒冷地において着火性が低下 する傾向にある。また、従来の軽油の場合、低温流動性が不十分となりやすぐ前述 の低 、着火性と相まって、低温始動性などの運転性能が低下する傾向にある。  [0005] For example, in terms of fuel efficiency, ignitability tends to decrease particularly in winter or in cold regions. In addition, in the case of conventional light oil, low-temperature fluidity becomes insufficient, and immediately, the above-mentioned low and ignitability tend to decrease operating performance such as low-temperature startability.
[0006] また、着火点及び低温流動性を改善する方法としては軽油の軽質ィ匕が考えられる 。軽油の軽質化は、ゴム製部材の耐久性の向上の点でも有効である。しかし、単に軽 油を軽質ィ匕するだけでは、エンジン性能における燃費や出力などの、ディーゼル燃 料としての本質的な品質に支障を来すおそれがある。 [0007] 本発明は、このような実情に鑑みてなされたものであり、その目的は、着火性及び 低温流動性に優れ、冬季又は寒冷地にぉ 、て好適に使用可能な軽油組成物を提 供することを目的とする。また、本発明の他の目的は、ディーゼル燃料としての本質 的な品質を十分に維持しつつ、着火性及び低温流動性が改善された軽油組成物を 提供することを目的とする。 [0006] Further, as a method for improving the ignition point and low temperature fluidity, light oil soot can be considered. Lightening the light oil is also effective in improving the durability of the rubber member. However, simply lightening diesel oil may interfere with the essential quality of diesel fuel, such as fuel efficiency and output in engine performance. [0007] The present invention has been made in view of such circumstances, and an object of the present invention is to provide a light oil composition that is excellent in ignitability and low-temperature fluidity and that can be suitably used in winter or cold regions. The purpose is to provide. Another object of the present invention is to provide a light oil composition having improved ignitability and low-temperature fluidity while sufficiently maintaining the essential quality as a diesel fuel.
課題を解決するための手段  Means for solving the problem
[0008] 本発明者らは、上記目的を達成するために、先ず、ガスクロマトグラフ'飛行時間質 量分析計 (以下、「GC— TOFMS」と略す。)を用いて軽油の組成を分析し、その組 成が着火性及び低温流動性に及ぼす影響について検討した。その結果、特定の炭 素数の範囲におけるパラフィン組成が特定条件を満たすと共に、徐冷曇り点及び流 動点がそれぞれ特定条件を満たすようにすることによって、軽油組成物の着火性及 び低温流動性を飛躍的に向上できることを見出し、本発明を完成するに至った。  [0008] In order to achieve the above object, the present inventors first analyzed the composition of light oil using a gas chromatograph 'time-of-flight mass spectrometer (hereinafter abbreviated as "GC-TOFMS"), The effect of the composition on ignitability and low-temperature fluidity was investigated. As a result, the paraffin composition in the specific carbon number range satisfies the specific conditions, and the gradual cooling cloud point and the pour point satisfy the specific conditions, respectively. As a result, the present invention has been completed.
[0009] すなわち、本発明は、炭素数 10〜24のパラフィンの組成が下記式(1— 1)で表さ れる条件を満たし、徐冷曇り点が 6. 0°C以下であり、かつ、  That is, in the present invention, the composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-1), the slow cooling cloud point is 6.0 ° C. or less, and
流動点が 7. 5°C以下であることを特徴とする軽油組成物(以下、便宜的に「第 1 の軽油組成物」 t 、う。)を提供する。  A gas oil composition having a pour point of 7.5 ° C. or less (hereinafter referred to as “first gas oil composition” t, for convenience) is provided.
[数 1]  [Number 1]
24  twenty four
340.0 f(n) < 400.0 (1 - 1)  340.0 f (n) <400.0 (1-1)
«=ιο  «= Ιο
[式(1— 1)中、 nはパラフィンの炭素数を示し、 f (n)は下記式(2):  [In the formula (1-1), n represents the carbon number of paraffin, and f (n) represents the following formula (2):
[数 2]  [Equation 2]
/(") = 27.45 - 3.55 I a)― 0.65(c I a) (2) / (") = 27.45-3.55 I a) ― 0.65 (c I a) (2)
(nは 10〜24の整数を示し、 a、 b及び cはそれぞれ炭素数 nのパラフィンの全量に占 める炭素数 nのノルマルパラフィン、炭素数 nの 1分岐のイソパラフィン及び炭素数 n の 2分岐以上のイソパラフィンの割合 (モル換算値)を示す。 ) (n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
で表される炭素数 nのパラフィン組成パラメータを示す。 ]  The paraffin composition parameter of carbon number n represented by these is shown. ]
[0010] このように、炭素数が同一であるノルマルパラフィン、 1分岐のイソパラフィン及び 2 分岐以上のイソパラフィンの割合に基づ 、て得られるパラフィン組成パラメータ f (n) を指標とし、炭素数 10〜24における f (n)の合計量 (上記式(1— 1)の中辺)を 340. 0-400. 0の範囲内とし、さらに徐冷曇り点を 6. 0°C以下、流動点を 7. 5°C以 下とすることで、着火性及び低温流動性の双方を飛躍的に改善することができ、その 結果、冬季又は寒冷地において好適に使用可能な軽油組成物を実現することが可 能となる。 [0010] Thus, the paraffin composition parameter f (n) obtained based on the ratio of normal paraffin having the same carbon number, one-branched isoparaffin, and two or more branch-isoparaffins. And the total amount of f (n) in the C10-24 range (middle side of the above formula (1-1)) is in the range of 34.0 to 40.0, and the slow cooling cloud point is 6. By setting the pour point to 0 ° C or less and the pour point to 7.5 ° C or less, both ignitability and low-temperature fluidity can be drastically improved, and as a result, it can be used favorably in winter or cold regions. It is possible to realize a simple light oil composition.
ここで、式(2)中の(bZa)及び (cZa)、すなわち各炭素数におけるノルマルパラフ インに対する 1分岐のイソパラフィン及び 2分岐以上のイソパラフィンのモル比は、上 述の通り GC— TOFMSを用いて得ることができる。 GC— TOFMSにおいては、先 ず、試料の構成成分をガスクロマトグラフィーにより分離し、分離された各成分をィォ ン化する。次いで、イオンに一定の加速電圧を与えたときの飛行速度力 Sイオンの質量 によって異なることに基づき、イオンを質量分離し、イオン検出器への到達時間の違 いに基づいて質量スペクトルを得る。なお、 GC—TOFMSにおけるイオン化法として は、フラグメントイオンの生成を抑制し、ノラフィン組成の測定精度をより向上させるこ とができることから、 FIイオンィ匕法が好ましい。本発明における測定装置及び測定条 件を以下に示す。  Here, (bZa) and (cZa) in formula (2), that is, the molar ratio of 1-branched isoparaffin and 2 or more-branched isoparaffin to normal paraffin at each carbon number is determined using GC-TOFMS as described above. Obtainable. In GC-TOFMS, the sample components are first separated by gas chromatography, and each separated component is ionized. Next, based on the fact that the ion velocity is different depending on the mass of the flying velocity force S ions when a constant acceleration voltage is applied to the ions, the ions are mass separated, and a mass spectrum is obtained based on the difference in arrival time to the ion detector. As the ionization method in GC-TOFMS, the FI ionization method is preferable because it can suppress the generation of fragment ions and can further improve the measurement accuracy of the norafine composition. The measurement apparatus and measurement conditions in the present invention are shown below.
(GC咅 (GC 咅
装置: HEWLETT PACKARD製、 HP6890 Series GC System & Inject or Instrument: HEWLETT PACKARD, HP6890 Series GC System & Inject or
カラム: A glient HP— 5 (30mX 0. 32mm , 0. 25 ^ m- film) Column: A glient HP— 5 (30mX 0.32mm, 0.25 ^ m-film)
キャリアガス: He、 1. 4mLZ分(一定流量) Carrier gas: He, 1.4 mLZ min (constant flow)
注入口温度: 320°C Inlet temperature: 320 ° C
注入モード:スプリット(スプリット比 = 1: 100) Injection mode: Split (split ratio = 1: 100)
オーブン温度: 50°Cにて 5分間保持し、 5°CZ分で昇温し、 320°Cにて 6分間保持す る Oven temperature: Hold at 50 ° C for 5 minutes, heat up at 5 ° CZ, and hold at 320 ° C for 6 minutes
注入量:1 Injection volume: 1
(TOFMS部) (TOFMS Department)
装置:日本電子製、 JMS— T100GC Equipment: JEOL JMS-T100GC
対抗電極電圧: 10. OkV イオン化法: FI+ (電界イオン化) Counter electrode voltage: 10. OkV Ionization method: FI + (field ionization)
GCインターフェース温度: 250°C  GC interface temperature: 250 ° C
測定質量範囲: 35〜500。  Measurement mass range: 35-500.
[0012] そして、上記の測定データに基づき、炭素数が同一である成分ごとに、ノルマルバ ラフィンの強度の合計に対して、 1分岐のイソパラフィンの強度の合計及び 2分岐以 上のイソパラフィンの強度の合計の比を求めることによって、ノルマルパラフィンに対 する 1分岐のイソパラフィン及び 2分岐以上のイソパラフィンのモル比を得ることができ る。なお、当該モル比は質量スペクトルから直接求めてもよいが、質量スペクトルデー タに基づいて、炭素数が同一である成分ごとにガスクロマトグラフィーのリテンションタ ィムと強度との相関を示すグラフを作成し、そのグラフにおける各成分のピーク面積 比をモル比としてもよい。  [0012] Based on the above measurement data, for each component having the same carbon number, the total strength of one-paraffin and the strength of isoparaffins with two or more branches are compared to the total strength of normal paraffin. By determining the total ratio, it is possible to obtain the molar ratio of 1-branched isoparaffin and 2 or more-branched isoparaffin to normal paraffin. The molar ratio may be obtained directly from the mass spectrum, but based on the mass spectrum data, a graph showing the correlation between the retention time and the intensity of gas chromatography for each component having the same carbon number. The peak area ratio of each component in the graph may be a molar ratio.
[0013] 図 1は炭素数が同一である成分のガスクロマトグラフィーのリテンションタイムと強度 との相関の一例を示すグラフである。図 1中、領域 A、 B、 Cのピークはそれぞれノル マルパラフィン、 1分岐のイソパラフィン、 2分岐以上のイソパラフィンに対応するピー クである。そして、本発明で規定するノルマルパラフィンに対する 1分岐のイソパラフィ ンのモル比 (bZa)は、領域 Aのピーク面積 S に対する領域 Bのピーク面積 S の比(  [0013] FIG. 1 is a graph showing an example of the correlation between retention time and intensity of gas chromatography of components having the same carbon number. In Fig. 1, the peaks in regions A, B, and C correspond to normal paraffin, one-branch isoparaffin, and two or more branch isoparaffins, respectively. The molar ratio (bZa) of the one-branched isoparaffin to the normal paraffin defined in the present invention is the ratio of the peak area S of the region B to the peak area S of the region A (
A B  A B
S /S )として求められる。また、ノルマルパラフィンに対する 2分岐以上のイソバラフ S / S). In addition, isoparaffin with 2 or more branches to normal paraffin
B A B A
インのモル比(cZa)は、領域 Aのピーク面積 S に対する領域 Cのピーク面積 Sの比  The molar ratio of in (cZa) is the ratio of the peak area S of region C to the peak area S of region A
A c A c
(S /S )として求められる。 It is calculated as (S / S).
c A  c A
[0014] なお、従来の軽油の開発においては、上記特許文献 1に記載されているように、ノ ルマルパラフィンとイソパラフィンとの比を指標とするに留まっており、イソパラフィンの 分岐数に着目してその組成を検討した例はほとんどない。このような従来の技術水準 からみて、上記第 1の軽油組成物は、軽油の着火性及び低温流動性の指標としてノ ルマルパラフィンに対する 1分岐のイソパラフィン及び 2分岐以上のイソパラフィンの モル比に基づくパラフィン組成パラメータ f (n)が好適であり、 f (n)を求める手法として GC— TOFMSが有用であるという本発明者らの知見に基づいて初めてなされるもの であり、また、本発明による上述の効果も極めて予想外の効果であるといえる。  [0014] In the development of conventional light oil, as described in Patent Document 1 above, the ratio of normal paraffin to isoparaffin is used as an index, and attention is paid to the number of branches of isoparaffin. Few examples have examined the composition. In view of such a conventional technical level, the first light oil composition is a paraffin based on a molar ratio of one-branch isoparaffin and two-branch or more isoparaffins to normal paraffin as an index of light oil ignitability and low-temperature fluidity. The composition parameter f (n) is suitable, and is first made based on the knowledge of the present inventors that GC-TOFMS is useful as a method for obtaining f (n). It can be said that the effect is extremely unexpected.
[0015] また、上記第 1の軽油組成物においては、セタン価が 65以上であり、硫黄含有量が 10質量 ppm以下であり、芳香族分の含有量が 1質量%以下であり、ナフテン分の含 有量が 5質量%以下であり、目詰まり点が 5°C以下であることがそれぞれ好ましい。 [0015] Further, in the first light oil composition, the cetane number is 65 or more, and the sulfur content is It is preferable that the content is 10 mass ppm or less, the aromatic content is 1 mass% or less, the naphthene content is 5 mass% or less, and the clogging point is 5 ° C. or less.
[0016] また、本発明は、炭素数 10〜24のパラフィンの組成が下記式(1— 2)で表される条 件を満たし、留出温度 250°Cにおける留出量 E250が 5〜45%であり、かつ、徐冷曇 り点が 6. 0°Cを超えることを特徴とする軽油組成物(以下、便宜的に「第 2の軽油 組成物」という。)を提供する。 [0016] In the present invention, the composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-2), and the distillation amount E250 at a distillation temperature of 250 ° C is 5 to 45. And a light oil composition (hereinafter referred to as “second light oil composition” for the sake of convenience) having a slow clouding point of more than 6.0 ° C.
[数 3]  [Equation 3]
24  twenty four
370.0 < /(^) < 430.0 (1 - 2) 370.0 </ (^) <430.0 (1-2)
Figure imgf000007_0001
Figure imgf000007_0001
[式(1— 2)中、 nはパラフィンの炭素数を示し、 f (n)は下記式(2):  [In the formula (1-2), n represents the carbon number of paraffin, and f (n) represents the following formula (2):
画 («) = 27.45 - 3.55( I a) - 0.65(c I a) (2)  («) = 27.45-3.55 (I a)-0.65 (c I a) (2)
(nは 10〜24の整数を示し、 a、 b及び cはそれぞれ炭素数 nのパラフィンの全量に占 める炭素数 nのノルマルパラフィン、炭素数 nの 1分岐のイソパラフィン及び炭素数 n の 2分岐以上のイソパラフィンの割合 (モル換算値)を示す。 ) (n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
で表される炭素数 nのパラフィン組成パラメータを示す。 ]  The paraffin composition parameter of carbon number n represented by these is shown. ]
[0017] このように、炭素数が同一であるノルマルパラフィン、 1分岐のイソパラフィン及び 2 分岐以上のイソパラフィンの割合に基づ 、て得られるパラフィン組成パラメータ f (n) を指標とし、炭素数 10〜24における f (n)の合計量 (上記式(1— 1)の中辺)を 370. 0-430. 0の範囲内とし、さらに E250及び徐冷曇り点がそれぞれ上記条件を満た すようにすることで、ディーゼル燃料としての本質的な品質を十分に維持しつつ、着 火性及び低温流動性が改善された軽油組成物が実現可能となる。このように優れた 特性を有する上記第 2の軽油組成物は、特に夏季用ディーゼル燃料として好適であ る。 [0017] As described above, the paraffin composition parameter f (n) obtained based on the ratio of normal paraffin having the same carbon number, one-branched isoparaffin, and two-branch or higher isoparaffin is used as an index, and the carbon number of 10 to The total amount of f (n) in 24 (the middle side of the above formula (1-1)) is within the range of 37.0 to 43.0, and the E250 and the slow cooling cloud point satisfy the above conditions. By doing so, it is possible to realize a light oil composition with improved ignitability and low-temperature fluidity while sufficiently maintaining the essential quality as a diesel fuel. The second light oil composition having such excellent characteristics is particularly suitable as a summer diesel fuel.
[0018] なお、各炭素数における 1分岐のイソパラフィンに対する 2分岐以上のイソパラフィ ンのモル比の測定方法は、上記第 1の軽油組成物の場合と同様であるため、ここで は重複する説明を省略する。  [0018] The method for measuring the molar ratio of two or more branched isoparaffins to one branched isoparaffin at each carbon number is the same as that in the case of the first light oil composition, and therefore, redundant explanation is provided here. Omitted.
[0019] また、本発明でいう「E250」とは、 JIS K 2254「石油製品 蒸留試験方法 常 圧法」により得られる蒸留曲線力 算出される留出温度 250°Cにおける留出量を意 味する。 In addition, “E250” in the present invention means JIS K 2254 “Petroleum product distillation test method The distillation curve force obtained by the “pressure method” means the distillation volume at a distillation temperature of 250 ° C.
[0020] また、上記第 2の軽油組成物においては、セタン価が 65以上であり、硫黄含有量が 10質量 ppm以下であり、芳香族分の含有量が 1質量%以下であり、ナフテン分の含 有量が 5質量%以下であり、目詰まり点が 5°C以下であることがそれぞれ好ましい。 発明の効果  [0020] In the second light oil composition, the cetane number is 65 or more, the sulfur content is 10 mass ppm or less, the aromatic content is 1 mass% or less, and the naphthene content is The content of is preferably 5% by mass or less, and the clogging point is preferably 5 ° C. or less. The invention's effect
[0021] 本発明によれば、着火性及び低温流動性に優れ、冬季又は寒冷地にぉ 、て好適 に使用可能な軽油組成物が提供される。また、本発明によれば、ディーゼル燃料とし ての本質的な品質を十分に維持しつつ、着火性及び低温流動性が改善された軽油 組成物が提供される。  [0021] According to the present invention, there is provided a light oil composition that is excellent in ignitability and low-temperature fluidity and can be suitably used in winter or in cold regions. In addition, according to the present invention, a light oil composition having improved ignitability and low-temperature fluidity while sufficiently maintaining the essential quality as a diesel fuel is provided.
図面の簡単な説明  Brief Description of Drawings
[0022] [図 l]GC—TOFMSを用いて得られる、炭素数が同一である成分のガスクロマトダラ フィ一のリテンションタイムと強度との相関の一例を示すグラフである。  [0022] FIG. 1 is a graph showing an example of the correlation between the retention time and intensity of a gas chromatograph of components having the same carbon number, obtained using GC-TOFMS.
[図 2]燃費試験における運転モード (時間と車速との関係)を示すグラフである。 発明を実施するための最良の形態  FIG. 2 is a graph showing an operation mode (relationship between time and vehicle speed) in a fuel consumption test. BEST MODE FOR CARRYING OUT THE INVENTION
[0023] 以下、本発明の好適な実施形態について詳細に説明する。 [0023] Hereinafter, preferred embodiments of the present invention will be described in detail.
[0024] (第 1実施形態) [0024] (First embodiment)
本発明の第 1実施形態に係る軽油組成物は、下記条件 (A—l)、 ^ 1)及び(じ The light oil composition according to the first embodiment of the present invention comprises the following conditions (A-l), ^ 1) and
- 1)を満たすことを特徴とする。 -It is characterized by satisfying 1).
(A- 1)炭素数 10〜24のパラフィンの組成が下記式(1— 1)で表される条件を満す こと。  (A-1) The composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-1).
[数 5]  [Equation 5]
24  twenty four
340.0≤ f(n) < 400.0 (1 - 1)  340.0≤ f (n) <400.0 (1-1)
«=ιο  «= Ιο
[式(1— 1)中、 nはパラフィンの炭素数を示し、 f (n)は下記式(2):  [In the formula (1-1), n represents the carbon number of paraffin, and f (n) represents the following formula (2):
[数 6] («) = 27.45 - 3.55 I - 0.65(c I a) (2) (nは 10〜24の整数を示し、 a、 b及び cはそれぞれ炭素数 nのパラフィンの全量に占 める炭素数 nのノルマルパラフィン、炭素数 nの 1分岐のイソパラフィン及び炭素数 n の 2分岐以上のイソパラフィンの割合 (モル換算値)を示す。 ) [Equation 6] («) = 27.45-3.55 I-0.65 (c I a) (2) (n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins above branching (molar equivalent).)
で表される炭素数 nのパラフィン組成パラメータを示す。 ]  The paraffin composition parameter of carbon number n represented by these is shown. ]
(B— 1)徐冷曇り点が 6. 0°C以下であること。  (B— 1) Slow cooling cloud point is 6.0 ° C or less.
(C 1)流動点が 7. 5°C以下であること。  (C 1) The pour point should be 7.5 ° C or less.
[0025] 上記条件 (A— 1)に関し、炭素数 10〜24の範囲における f (n)の合計 (上記式(1 —1)中の中辺)は、前述の通り 340. 0〜400. 0であり、好ましくは 360. 0〜390. 0 、より好ましくは 370. 0〜390. 0、更に好ましくは 375. 0〜388. 0である。炭素数 1 0〜24の範囲における f (n)の合計が 340. 0未満であると容量発熱量が低くなつて 容量あたりの燃費が大幅に低下してしまい、また、 400. 0を超えると粘度が増加して しま 、適切な噴射制御ができなくなる。  [0025] Regarding the above condition (A-1), the sum of f (n) in the range of 10 to 24 carbon atoms (the middle side in the above formula (1-1)) is 34.0 to 400. 0, preferably 360.0 to 390.0, more preferably 370.0 to 390.0, and still more preferably 375.0 to 388.0. If the sum of f (n) in the range of carbon numbers from 10 to 24 is less than 340.0, the calorific value of the capacity will be low and the fuel consumption per capacity will be greatly reduced. Viscosity will increase and proper jetting control will not be possible.
[0026] また、第 1実施形態に係る軽油組成物における芳香族分の含有量は特に制限され ないが、 PM等の生成を抑制する点から、組成物全量を基準として、好ましくは 15容 量%以下、より好ましくは 10容量%以下、更に好ましくは 5容量%以下、特に好ましく は 1容量%以下である。なお、本発明でいう「芳香族分の含有量」とは、社団法人石 油学会により発行されて 、る石油学会誌 JPI— 5S— 49 97「炭化水素タイプ試験法 高速液体クロマトグラフ法」に準拠して測定される芳香族分含有量の容量百分率( 容量%)を意味する。  [0026] The aromatic content in the light oil composition according to the first embodiment is not particularly limited, but is preferably 15 volumes based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. % Or less, more preferably 10% by volume or less, still more preferably 5% by volume or less, and particularly preferably 1% by volume or less. “Aromatic content” as used in the present invention refers to JPI-5S-49 97 “Hydrocarbon type test method high-performance liquid chromatographic method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content measured according to the standard.
[0027] また、第 1実施形態に係る軽油組成物におけるナフテン分の含有量は特に制限さ れないが、 PM等の生成を抑制する点から、組成物全量を基準として、好ましくは 50 容量%以下、より好ましくは 30容量%以下、更に好ましくは 15容量%以下、特に好 ましくは 10容量%以下である。なお、本発明でいう「芳香族分の含有量」とは、 AST M D2425"Standard Test Method for Hydrocarbon Types in Middl e Distillates by Mass Spectrometry"に準拠して測定されるナフテン分の質 量百分率 (質量%)を意味する。  [0027] Further, the content of the naphthene in the light oil composition according to the first embodiment is not particularly limited, but is preferably 50% by volume based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. Below, more preferably 30% by volume or less, still more preferably 15% by volume or less, and particularly preferably 10% by volume or less. The “aromatic content” as used in the present invention refers to the mass percentage (mass of naphthene) measured according to ASTM D2425 “Standard Test Method for Hydrocarbon Types in Middel Distillates by Mass Spectrometry”. %).
[0028] また、第 1実施形態に係る軽油組成物の硫黄分の含有量は、ディーゼル自動車の 排ガス後処理装置の浄ィ匕性能を良好に保持できることから、組成物全量を基準とし て、好ましくは 10質量 ppm以下であり、より好ましくは 5質量 ppm以下、より好ましくは 3質量 ppm以下、特に好ましくは 1質量 ppm以下である。なお、本発明でいう「硫黄 分の含有量」とは、 JIS K 2541「硫黄分試験方法」に準拠して測定される値を意味 する。 [0028] In addition, the sulfur content of the light oil composition according to the first embodiment is based on the total amount of the composition because the purification performance of the exhaust gas aftertreatment device of a diesel vehicle can be satisfactorily maintained. The amount is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, more preferably 3 ppm by mass or less, and particularly preferably 1 ppm by mass or less. The “sulfur content” in the present invention means a value measured according to JIS K 2541 “Sulfur content test method”.
[0029] また、上記条件 (B— 1)に関し、第 1実施形態に係る軽油組成物の徐冷曇り点は、 前述の通り 6. 0°C以下であり、好ましくは 7. 0°C以下、より好ましくは 7. 5°C以 下、更に好ましくは 8. 0°C以下である。徐冷曇り点が 7. 0°C以下であると、ディ ーゼル自動車の燃料噴射装置のフィルターにワックスが付着しても当該ワックスを容 易に溶解できる。なお、本発明でいう「徐冷曇り点」とは以下のようにして測定される 値を意味する。すなわち、底面がアルミニウム面である試料容器に厚さが 1. 5mmと なるように試料を入れ、容器の底面より 3mmの高さから光を照射する。この状態で、 曇り点よりも 10°C以上高い温度から 0. 5°CZ分で徐冷し、反射光の光量が照射光の 7Z8以下となる温度 (徐冷曇り点)を 0. 1°C単位で検知する。ここで、「曇り点」とは、 J IS K 2269「原油及び石油製品の流動点並びに石油製品曇り点試験方法」に準 拠して測定される曇り点を意味する。第 1実施形態に係る軽油組成物の曇り点は特 に制限されないが、好ましくは 0. 0°C以下であり、より好ましくは 2. 0°C以下、更に 好ましくは 5. 0°C以下、特に好ましくは 8. 0°C以下である。曇り点が 0°C以下で あると、ディーゼル自動車の燃料噴射装置のフィルターにワックスが付着しても当該 ワックスを容易に溶解できる傾向にある。  [0029] Regarding the above condition (B-1), the slow-cooling cloud point of the light oil composition according to the first embodiment is 6.0 ° C or less, preferably 7.0 ° C or less, as described above. More preferably, it is 7.5 ° C or less, and further preferably 8.0 ° C or less. If the slow-cooling cloud point is 7.0 ° C or lower, the wax can be easily dissolved even if it adheres to the filter of the fuel injection device of a diesel vehicle. The “slow cooling cloud point” in the present invention means a value measured as follows. In other words, put the sample in a sample container whose bottom is an aluminum surface so that the thickness is 1.5 mm, and irradiate light from a height of 3 mm from the bottom of the container. In this state, gradually cool from 0.5 ° CZ minutes at a temperature 10 ° C or higher above the cloud point, and set the temperature at which the amount of reflected light is 7Z8 or less of the irradiated light (slow cooling cloud point) to 0.1 °. Detect in C units. Here, the “cloud point” means a cloud point measured in accordance with J IS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”. The cloud point of the light oil composition according to the first embodiment is not particularly limited, but is preferably 0.0 ° C or less, more preferably 2.0 ° C or less, and even more preferably 5.0 ° C or less. Particularly preferably, it is 8.0 ° C or lower. If the cloud point is 0 ° C or less, even if wax adheres to the filter of the fuel injection device of a diesel vehicle, the wax tends to be easily dissolved.
[0030] また、上記条件 (C 1)に関し、第 1実施形態に係る軽油組成物の流動点は、前述 の通り— 7. 5°C以下であり、好ましくは— 10°C以下、より好ましくは— 15°C以下、更 に好ましくは— 20°C以下である。流動点を— 7. 5°C以下とすることで、ディーゼル自 動車における燃料ラインでの流動性を十分に確保することができる。なお、本発明で いう「流動点」とは、 JIS K 2269「原油及び石油製品の流動点並びに石油製品曇 り点試験方法」に準拠して測定される流動点を意味する。  [0030] Regarding the above condition (C1), the pour point of the light oil composition according to the first embodiment is −7.5 ° C. or lower as described above, preferably −10 ° C. or lower, and more preferably. Is −15 ° C. or lower, more preferably −20 ° C. or lower. By setting the pour point to -7.5 ° C or less, sufficient fluidity in the fuel line of a diesel vehicle can be secured. The “pour point” in the present invention means a pour point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
[0031] 第 1実施形態に係る軽油組成物を構成する基材は、軽油組成物が上記条件 (A— 1)、(B— 1)、(C 1)を満たす限りにおいて特に制限されず、石油系軽油基材、石 油系灯油基材、合成系軽油基材及び合成系灯油基材のうちの 1種を単独で、または 2種以上を組み合わせて用いることができる。なお、 2種以上の基材を組み合わせて 用いる場合、各基材が単独で上記条件 (A— 1)、(B— 1)、(C 1)を満たす必要は なぐそれらを混合した後の軽油組成物が上記条件 (A—l)、(B— 1)、(C— 1)を満 たせばよい。 [0031] The base material constituting the light oil composition according to the first embodiment is not particularly limited as long as the light oil composition satisfies the above conditions (A-1), (B-1), (C1), One of petroleum gas oil base, petroleum oil kerosene base, synthetic light oil base and synthetic kerosene base alone, or Two or more types can be used in combination. When two or more types of base materials are used in combination, each base material does not need to satisfy the above conditions (A-1), (B-1), (C1) alone. The composition may satisfy the above conditions (A-1), (B-1), and (C-1).
[0032] 本発明において使用される石油系軽油基材としては、具体的には例えば、原油の 常圧蒸留装置から得られる直留軽油;常圧蒸留装置から得られる直留重質油や残 查油を減圧蒸留装置にかけて得られる減圧軽油;直留軽油又は減圧軽油を水素化 精製して得られる水素化精製軽油;直留軽油を又は減圧軽油を通常の水素化精製 より苛酷な条件で一段階又は多段階で水素化脱硫して得られる水素化脱硫軽油;上 記の種々の軽油基材を水素化分解して得られる水素化分解軽油などが挙げられる。  [0032] Specific examples of the petroleum-based light oil base used in the present invention include straight-run gas oil obtained from a crude oil atmospheric distillation apparatus; straight-run heavy oil obtained from an atmospheric distillation apparatus and residual Vacuum gas oil obtained by subjecting koji oil to vacuum distillation equipment; hydrorefined gas oil obtained by hydrorefining straight-run gas oil or vacuum gas oil; straight-run gas oil or vacuum gas oil under normal conditions. Hydrodesulfurized diesel oil obtained by hydrodesulfurization in stages or multistages; hydrocracked diesel oil obtained by hydrocracking the above various diesel oil bases, and the like.
[0033] また、石油系灯油基材としては、具体的には例えば、原油の常圧蒸留装置から得 られる直留灯油;常圧蒸留装置から得られる直留重質油や残查油を減圧蒸留装置 にかけて得られる減圧灯油;直留灯油又は減圧灯油を水素化精製して得られる水素 化精製灯油;直留灯油を又は減圧灯油を通常の水素化精製より苛酷な条件で一段 階又は多段階で水素化脱硫して得られる水素化脱硫灯油;上記の種々の灯油基材 を水素化分解して得られる水素化分解灯油などが挙げられる。  [0033] As the petroleum-based kerosene base material, specifically, for example, straight-run kerosene obtained from a crude oil atmospheric distillation apparatus; straight-run heavy oil or residual oil obtained from an atmospheric distillation apparatus is decompressed. Depressurized kerosene obtained by distillation equipment; hydrorefined kerosene obtained by hydrorefining straight-run kerosene or depressurized kerosene; straight-run kerosene or depressurized kerosene in one stage or multiple stages under conditions severer than ordinary hydrorefining And hydrodesulfurized kerosene obtained by hydrocracking the above-mentioned various kerosene base materials.
[0034] なお、本発明において、石油系軽油基材又は石油系灯油基材を用いる場合、これ らの石油系基材を製造する際の各種処理条件は適宜選定することができる。例えば 水素化脱硫の際の水素分圧は、 IMPa以上が好ましぐ 3MPa以上がより好ましぐ 5 MPa以上が特に好ましい。また、水素分圧の上限は特に制限されないが、反応器の 耐圧力性の観点から、 lOMPa以下が好ましい。また、水素化脱硫の際の反応温度 は、 300°C以上が好ましぐ 320°C以上がより好ましぐ 340°C以上が特に好ましい。 また、反応温度の上限は特に制限されないが、反応器の耐熱性の観点から、 400°C 以下が好ましい。また、水素化脱硫の際の液空間速度は、 6h_1以下が好ましぐ 4h" 1以下がより好ましぐ 2h_ 1以下が特に好ましい。また、液空間速度の下限は特に制 限されないが、偏流の観点から、 0. lh_1以上が好ましい。また、上記水素化脱硫に 使用される触媒としては、特に限定されるものではないが、 Ni、 Co、 Mo、 W、 Pd、 Pt などの金属を 2〜3種類組み合わせて用いるものを挙げることができる。具体的には、 Co— Mo系、 Ni— Mo系、 Ni— Co— Mo系、 Ni—W系等の触媒を好ましく用いるこ と力でき、中でも汎用性の点から、 Co— Mo系、 Ni—Mo系の触媒がより好ましい。 In the present invention, when a petroleum light oil base or a petroleum kerosene base is used, various processing conditions for producing these petroleum bases can be appropriately selected. For example, the hydrogen partial pressure during hydrodesulfurization is particularly preferably 5 MPa or more, more preferably 3 MPa or more, more preferably IMPa or more. In addition, the upper limit of the hydrogen partial pressure is not particularly limited, but is preferably lOMPa or less from the viewpoint of pressure resistance of the reactor. The reaction temperature during hydrodesulfurization is preferably 300 ° C or higher, more preferably 320 ° C or higher, and particularly preferably 340 ° C or higher. The upper limit of the reaction temperature is not particularly limited, but is preferably 400 ° C. or lower from the viewpoint of heat resistance of the reactor. The liquid hourly space velocity during hydrodesulfurization, 6h _1 less preferred instrument 4h "1 or less and more preferably tool 2h _ 1 or less is particularly preferred. Further, the lower limit of the liquid hourly space velocity is not particularly restricted From the viewpoint of drift, 0.1 lh _1 or more is preferable, and the catalyst used in the hydrodesulfurization is not particularly limited, but Ni, Co, Mo, W, Pd, Pt, etc. Examples include using two or three kinds of metals in combination. Co-Mo-based, Ni-Mo-based, Ni-Co-Mo-based, and Ni-W-based catalysts can be preferably used. From the viewpoint of versatility, Co-Mo-based and Ni-Mo-based catalysts can be used. Is more preferable.
[0035] また、「合成系軽油基材」とは、天然ガス、アスファルト分、石炭等を原料とし、これを 化学合成させることで得られる軽油基材を ヽぅ。化学合成方法としては間接液化法、 直接液ィ匕法などがあり、代表的な合成手法として、フィッシャー 'トロプシュ合成法が 挙げられるが、本発明で使用する合成系軽油基材はこれらの製造方法により限定さ れるものではない。合成系軽油基材は一般に飽和炭化水素類が主成分であり、詳し くはノルマルパラフィン類、イソパラフィン類、ナフテン類力も構成されている。すなわ ち合成系軽油基材は一般に、芳香族分をほとんど含有していない。従って、軽油組 成物の芳香族分含有量を低減する場合には合成系軽油基材を用いることが好まし い。 [0035] The "synthetic light oil base material" is a light oil base material obtained by chemically synthesizing natural gas, asphalt content, coal, etc. as raw materials. Chemical synthesis methods include indirect liquefaction method and direct liquid solution method, and the typical synthesis method is Fischer's Tropsch synthesis method. It is not limited by. Synthetic light oil bases are generally composed of saturated hydrocarbons, and more specifically, normal paraffins, isoparaffins, and naphthenes. That is, a synthetic light oil base generally contains almost no aromatic content. Therefore, when reducing the aromatic content of the light oil composition, it is preferable to use a synthetic light oil base.
[0036] また、「合成系灯油基材」とは、天然ガス、アスファルト分、石炭等を原料とし、これを 化学合成させることで得られる灯油基材を ヽぅ。化学合成方法としては間接液化法、 直接液ィ匕法などがあり、代表的な合成手法として、フィッシャー 'トロプシュ合成法が 挙げられるが、本発明で使用する合成系灯油基材はこれらの製造方法により限定さ れるものではない。合成系灯油基材は一般に飽和炭化水素類が主成分であり、詳し くはノルマルパラフィン類、イソパラフィン類、ナフテン類力も構成されている。すなわ ち合成系灯油基材は一般に、芳香族分をほとんど含有していない。従って、軽油組 成物の芳香族分含有量を低減する場合には合成系灯油基材を用いることが好まし い。  [0036] The "synthetic kerosene base" is a kerosene base obtained by chemically synthesizing natural gas, asphalt, coal, and the like as raw materials. Chemical synthesis methods include indirect liquefaction method and direct liquid solution method, and the typical synthesis method is Fischer's Tropsch synthesis method. The synthetic kerosene base material used in the present invention is a production method of these. It is not limited by. Synthetic kerosene bases are generally composed of saturated hydrocarbons, and more specifically, normal paraffins, isoparaffins, and naphthenes. That is, the synthetic kerosene base material generally contains almost no aromatic content. Therefore, it is preferable to use a synthetic kerosene base material to reduce the aromatic content of the light oil composition.
[0037] 第 1実施形態に係る軽油組成物は、上記の石油系基材及び Z又は合成系基材の うちの 1種又は 2種以上を含有することができるが、それらの中でも、硫黄分や芳香族 分と 、つた環境負荷を増加させる頻度を低減する点から、合成系軽油基材及び Z又 は合成系灯油基材を必須成分として含有することが好ま ヽ。合成系軽油基材及び Z又は合成系灯油基材の含有量の合計は、組成物全量を基準として、 20容量%以 上であることが好ましぐ 30容量%以上であることがより好ましぐ 40容量%以上であ ることが更に好ましぐ 50容量%以上であることが特に好ましい。  [0037] The light oil composition according to the first embodiment may contain one or more of the above petroleum-based substrates and Z or synthetic-based substrates, and among them, the sulfur content It is preferable to contain a synthetic light oil base material and a Z or synthetic kerosene base material as essential components from the viewpoint of reducing the frequency of increasing the environmental load, and aromatic components. The total content of the synthetic light oil base and the Z or synthetic kerosene base is preferably 20% by volume or more, more preferably 30% by volume or more, based on the total amount of the composition. More preferably, it is more preferably 40% by volume or more, and particularly preferably 50% by volume or more.
[0038] また、第 1実施形態に係る軽油組成物は上記の軽油基材及び Z又は灯油基材の みで構成されてもよいが、必要に応じて低温流動性向上剤を含有することができる。 低温流動性向上剤としては、具体的には、エチレン—酢酸ビニル共重合体に代表さ れるエチレン 不飽和エステル共重合体、ァルケ-ルコハク酸アミド、ポリエチレング リコールのジべヘン酸エステルなどの線状の化合物、アルキルフマレートまたはアル キルイタコネ一トー不飽和エステル共重合体など力 なるくし形ポリマーなどの低温 流動性向上剤、フタル酸、コハク酸、エチレンジァミン四酢酸、ユトリロ酢酸などの酸 またはその酸無水物などとヒドロカルビル置換ァミンなどとの反応生成物など力 なる 極性窒素化合物を含有する低温流動性向上剤などを挙げることができ、これらの化 合物の 1種または 2種以上を組み合わせて使用してもよい。この中でも汎用性の観点 から、エチレン 酢酸ビニル共重合体系添加剤、極性窒素化合物を含有する低温 流動性向上剤を好ましく使用することができ、ワックス結晶微細化促進および、ヮック スの凝集沈降を防止する点で、極性窒素化合物を含有する低温流動性向上剤の使 用がさらに好ましい。 [0038] Further, the light oil composition according to the first embodiment comprises the above light oil base material and Z or kerosene base material. However, it may contain a low temperature fluidity improver if necessary. Specific examples of the low temperature fluidity improver include ethylene unsaturated ester copolymers typified by ethylene-vinyl acetate copolymers, alkenyl succinic acid amides, polyethylene glycol dibehenate esters, and the like. Low-temperature fluidity improver such as a strong comb-like polymer such as an alkyl fumarate or an alkyl fumarate unsaturated alkyl ester copolymer, an acid such as phthalic acid, succinic acid, ethylene diammine tetraacetic acid, utlyloacetic acid Examples include reaction products of anhydrides and hydrocarbyl-substituted amines, and other low-temperature fluidity improvers containing polar nitrogen compounds. Use one or more of these compounds in combination. May be. Among these, from the viewpoint of versatility, an ethylene vinyl acetate copolymer additive and a low-temperature fluidity improver containing a polar nitrogen compound can be preferably used to prevent wax crystal refinement and prevent coagulation sedimentation of wax. Therefore, it is more preferable to use a low temperature fluidity improver containing a polar nitrogen compound.
[0039] 低温流動性向上剤の含有量は、組成物全量を基準として、好ましくは 50〜500mg ZL、より好ましくは 100〜300mgZLである。低温流動性向上剤の含有量が前記 下限値未満であると、その添カ卩による低温流動性向上効果が不十分となる傾向にあ る。また、低温流動性向上剤の含有量が前記上限値を超えても、含有量に見合う低 温流動性の更なる向上効果は得られな 、傾向にある。  [0039] The content of the low-temperature fluidity improver is preferably 50 to 500 mg ZL, more preferably 100 to 300 mg ZL, based on the total amount of the composition. If the content of the low temperature fluidity improver is less than the lower limit, the effect of improving the low temperature fluidity due to the additive tends to be insufficient. Further, even if the content of the low temperature fluidity improver exceeds the above upper limit, there is a tendency that a further improvement effect of the low temperature fluidity commensurate with the content cannot be obtained.
[0040] また、第 1実施形態に係る軽油組成物は、潤滑性向上剤を更に含有することができ る。潤滑性向上剤としては、エステル系、カルボン酸系、アルコール系、フエノール系 、アミン系等の潤滑性向上剤の 1種または 2種以上を使用することができる。この中で も、汎用性の観点から、エステル系、カルボン酸系の潤滑性向上剤の使用が好まし い。さらに添加濃度に対する添加効果が飽和に達しにくぐ HFRRの WS1. 4値をよ り小さくできる点からはエステル系潤滑性向上剤が好ましぐ添加濃度に対する添カロ 効果の初期応答性が高ぐ潤滑性向上剤の添加量を少なくできる可能性があるとい う点からはカルボン酸系潤滑性向上剤が好ましい。  [0040] Further, the light oil composition according to the first embodiment may further contain a lubricity improver. As the lubricity improver, one or more of lubricity improvers such as ester, carboxylic acid, alcohol, phenol, and amine can be used. Among these, from the viewpoint of versatility, it is preferable to use an ester-based or carboxylic acid-based lubricity improver. In addition, it is difficult for the additive effect to reach saturation. From the point that the WS1.4 value of HFRR can be made smaller, ester-based lubricity improvers are preferred. A carboxylic acid-based lubricity improver is preferable from the viewpoint that the addition amount of the property improver can be reduced.
[0041] エステル系の潤滑性向上剤としては、例えば、グリセリンのカルボン酸エステル等を 挙げることができ、具体的には、リノール酸、ォレイン酸、サリチル酸、ノルミチン酸、 ミリスチン酸、へキサデセン酸等のグリセリンエステルを挙げることができ、これらの 1 種または 2種以上を適宜使用することができる。 [0041] Examples of ester-based lubricity improvers include glycerin carboxylic acid esters and the like. Specifically, linoleic acid, oleic acid, salicylic acid, normitic acid, Examples thereof include glycerin esters such as myristic acid and hexadecenoic acid, and one or more of these can be used as appropriate.
[0042] 潤滑性向上剤の含有量は、組成物全量を基準として、好ましくは 25〜500mg/L 、より好ましくは 25〜300mgZL、更に好ましくは 25〜200mgZLである。潤滑性向 上剤の含有量が前記下限値未満であると、その添加による潤滑性向上効果が不十 分となる傾向にある。また、潤滑性向上剤の含有量が前記上限値を超えても、含有 量に見合う低温流動性の更なる向上効果は得られな 、傾向にある。  [0042] The content of the lubricity improver is preferably 25 to 500 mg / L, more preferably 25 to 300 mgZL, still more preferably 25 to 200 mgZL, based on the total amount of the composition. When the content of the lubricity improver is less than the lower limit, the effect of improving the lubricity due to the addition tends to be insufficient. Further, even if the content of the lubricity improver exceeds the above upper limit, there is a tendency that a further improvement effect of low temperature fluidity commensurate with the content cannot be obtained.
[0043] また、第 1実施形態に係る軽油組成物は、上記の低温流動性向上剤又は潤滑性 向上剤以外の添加剤を更に含有してもよい。力かる添加剤としては、アルケニルコハ ク酸誘導体、カルボン酸のアミン塩等の清浄剤、フエノール系、アミン系等の酸ィ匕防 止剤、サリチリデン誘導体等の金属不活性化剤、ポリダリコールエーテル等の氷結防 止剤、脂肪族ァミン、ァルケニルコハク酸エステル等の腐食防止剤、ァニオン系、力 チオン系、両性系界面活性剤等の帯電防止剤、ァゾ染料等の着色剤、シリコン系等 の消泡剤などを挙げることができる。これらの他の添加剤は、単独または数種類を組 み合わせて添加することができる。添加量も適宜選択することができる力 その他の 添加剤全量で、軽油組成物に対して、例えば、 0. 5質量%以下とすることができ、好 ましくは 0. 2質量%以下である。なお、ここでいう添カ卩量全量とは、添加剤の有効成 分としての添加量を意味して!/ヽる。  [0043] The light oil composition according to the first embodiment may further contain additives other than the low-temperature fluidity improver or the lubricity improver. Examples of powerful additives include detergents such as alkenyl succinic acid derivatives, carboxylic acid amine salts, phenolic and amine-based acid detergents, metal deactivators such as salicylidene derivatives, and polydaricol. Anti-icing agents such as ether, corrosion inhibitors such as aliphatic amines, alkenyl succinates, anti-static agents such as anionic, force thione, and amphoteric surfactants, coloring agents such as azo dyes, silicones, etc. An antifoaming agent can be mentioned. These other additives can be added singly or in combination of several kinds. Power that can be selected as appropriate Addition amount Other additives Total amount can be, for example, 0.5% by mass or less, and preferably 0.2% by mass or less, with respect to the light oil composition. . Here, the total amount of the additive added means the added amount as an effective component of the additive!
[0044] 第 1実施形態に係る軽油組成物は、各種性能の更なる改善の点から、上記条件 (A — 1)、(B—l)、(C—1)に加えて、以下に示す条件を満たすことが好ましい。  [0044] In addition to the above conditions (A-1), (Bl), and (C-1), the light oil composition according to the first embodiment is shown below from the viewpoint of further improving various performances. It is preferable to satisfy the conditions.
[0045] 第 1実施形態に係る軽油組成物のセタン指数は、着火性の観点から、好ましくは 6 5以上であり、より好ましくは 70以上、更に好ましくは 73以上、特に好ましくは 75以上 である。  [0045] From the viewpoint of ignitability, the cetane index of the light oil composition according to the first embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 73 or more, and particularly preferably 75 or more. .
[0046] また、第 1実施形態に係る軽油組成物のセタン価は、着火性の観点から、好ましく は 65以上であり、より好ましくは 70以上、更に好ましくは 73以上、特に好ましくは 75 以上である。  [0046] Further, from the viewpoint of ignitability, the cetane number of the light oil composition according to the first embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 73 or more, and particularly preferably 75 or more. is there.
[0047] なお、本発明でいう「セタン指数」及び「セタン価」とは、それぞれ JIS K 2280「石 油製品 燃料油 オクタン価及びセタン価試験方法並びにセタン指数算出方法」に 準拠して測定される値を意味する。 [0047] The "cetane index" and "cetane number" as used in the present invention refer to JIS K 2280 "petroleum oil fuel oil octane number and cetane number test method and cetane index calculation method", respectively. Means a value measured in compliance.
[0048] また、第 1実施形態に係る軽油組成物の目詰まり点は、ディーゼル自動車の燃料 噴射装置に設けられるフィルターの閉塞を抑制できることから、好ましくは 5°C以下 であり、より好ましくは 6°C以下、更に好ましくは 7°C以下、特に好ましくは 8°C 以下である。なお、本発明でいう「目詰まり点」とは、 JIS K 2288「石油製品—軽油 目詰まり点試験方法」に準拠して測定される値を意味する。  [0048] Further, the clogging point of the light oil composition according to the first embodiment is preferably 5 ° C or less, more preferably 6 because it can suppress the clogging of the filter provided in the fuel injection device of the diesel vehicle. ° C or lower, more preferably 7 ° C or lower, particularly preferably 8 ° C or lower. The “clogging point” in the present invention means a value measured in accordance with JIS K 2288 “Petroleum products—light oil clogging point test method”.
[0049] また、第 1実施形態に係る軽油組成物の 30°Cにおける動粘度は、好ましくは 1. 7m m2Zs以上、より好ましくは 2. 0mm2Zs以上、更に好ましくは 2. 3mm2Zs以上、特 に好ましくは 2. 5mm2Zs以上であり、また、好ましくは 5. 0mm2Zs以下、より好まし くは 4. 7mm2Zs以下、更に好ましくは 4. 5mm2Zs以下、特に好ましくは 4. 3mm2 Zs以下である。 30°Cにおける動粘度が前記下限値未満であると、ディーゼル自動 車において比較的高い温度下で使用された場合に、始動不良が起こりやすくなり、 また、アイドリング時のエンジンの回転が不安定ィ匕する傾向にある。他方、 30°Cにお ける動粘度が前記上限値を超えると、排ガス中の黒煙量が増大する傾向にある。な お、本発明でいう「30°Cにおける動粘度」とは、 JIS K 2283「原油及び石油製品— 動粘度試験方法及び粘度指数算出方法」に準拠して測定される値を意味する。 [0049] The kinematic viscosity at 30 ° C of the gas oil composition according to the first embodiment, preferably 1. 7m m 2 Zs or more, more preferably 2. 0 mm 2 Zs or more, more preferably 2. 3 mm 2 Zs or more, preferably in JP 2. 5 mm 2 Zs or more, and preferably 5. 0 mm 2 Zs, more rather preferably is 4. 7 mm 2 Zs less, more preferably 4. 5 mm 2 Zs less, particularly Preferably it is 4.3 mm 2 Zs or less. If the kinematic viscosity at 30 ° C is less than the above lower limit value, start-up failure is likely to occur when the diesel vehicle is used at a relatively high temperature, and engine rotation during idling is unstable. Tends to hesitate. On the other hand, when the kinematic viscosity at 30 ° C exceeds the upper limit, the amount of black smoke in the exhaust gas tends to increase. In the present invention, “kinematic viscosity at 30 ° C.” means a value measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
[0050] また、第 1実施形態に係る軽油組成物の引火点は、取り扱い時の安全性の点から、 好ましくは 45°C以上であり、より好ましくは 50°C以上、更に好ましくは 53°C以上、特 に好ましくは 55°C以上である。なお、本発明でいう「引火点」とは、 JIS K 2265「原 油及び石油製品 引火点試験方法」に準拠して測定される値を意味する。  [0050] The flash point of the light oil composition according to the first embodiment is preferably 45 ° C or higher, more preferably 50 ° C or higher, and still more preferably 53 °, from the viewpoint of safety during handling. C or higher, particularly preferably 55 ° C or higher. The “flash point” in the present invention means a value measured in accordance with JIS K 2265 “Flame point test method for crude oil and petroleum products”.
[0051] また、第 1実施形態に係る軽油組成物の蒸留性状に関し、その初留点(以下、「IB P」と略す。)は、好ましくは 140°C以上、より好ましくは 145°C以上、更に好ましくは 1 50°C以上、特に好ましくは 155°C以上であり、また、好ましくは 195°C以下、より好ま しくは 190°C以下、更に好ましくは 185°C以下、特に好ましくは 180°C以下である。 I BPが前記下限値未満であると、一部の軽質留分が気化し、ディーゼル自動車のェ ンジン内において噴霧範囲が広範囲となることに伴って排出ガス中の未燃の炭化水 素量が増大し、その結果、高温時の始動性及びアイドリング時のエンジンの回転の 安定性が低下する傾向にある。他方、 IBPが前記上限値を超えると、ディーゼル自動 車における低温時の始動性及び運転性が低下する傾向にある。 [0051] Further, regarding the distillation properties of the light oil composition according to the first embodiment, the initial boiling point (hereinafter abbreviated as "IB P") is preferably 140 ° C or higher, more preferably 145 ° C or higher. More preferably, it is 150 ° C or higher, particularly preferably 155 ° C or higher, preferably 195 ° C or lower, more preferably 190 ° C or lower, further preferably 185 ° C or lower, particularly preferably 180. It is below ° C. If I BP is less than the lower limit, some light fractions are vaporized, and the amount of unburned hydrocarbons in the exhaust gas increases as the spray range becomes wider within the diesel engine. As a result, the startability at high temperatures and the stability of engine rotation at idling tend to decrease. On the other hand, if IBP exceeds the upper limit, diesel automatic There is a tendency that startability and drivability at a low temperature in a vehicle are lowered.
[0052] また、第 1実施形態に係る軽油組成物の 10%留出温度 (以下、「T10」と略す。)は 、好ましくは 165°C以上、より好ましくは 170°C以上、更に好ましくは 175°C以上、特 に好ましくは 180°C以上であり、また、好ましくは 205°C以下、より好ましくは 200°C以 下、更に好ましくは 195°C以下、特に好ましくは 190°C以下である。 T10が前記下限 値未満であると、一部の軽質留分が気化し、ディーゼル自動車のエンジン内におい て噴霧範囲が広範囲となることに伴って排出ガス中の未年の炭化水素量が増大し、 その結果、高温時の始動性及びアイドリング時のエンジンの回転の安定性が低下す る傾向にある。他方、 T10が前記上限値を超えると、ディーゼル自動車における低温 時の始動性及び運転性が低下する傾向にある。  [0052] Further, the 10% distillation temperature (hereinafter abbreviated as "T10") of the light oil composition according to the first embodiment is preferably 165 ° C or higher, more preferably 170 ° C or higher, and still more preferably. 175 ° C or higher, particularly preferably 180 ° C or higher, preferably 205 ° C or lower, more preferably 200 ° C or lower, still more preferably 195 ° C or lower, particularly preferably 190 ° C or lower. is there. If T10 is less than the lower limit, some light fractions are vaporized, and the amount of hydrocarbons in the exhaust gas increases as the spray range becomes wider in the diesel engine. As a result, startability at high temperatures and engine rotation stability at idling tend to be reduced. On the other hand, when T10 exceeds the upper limit, the startability and drivability at low temperatures in a diesel vehicle tend to deteriorate.
[0053] また、第 1実施形態に係る軽油組成物の 50%留出温度(以下、「T50」と略す。 )は 、好ましくは 200°C以上、より好ましくは 205°C以上、更に好ましくは 210°C以上、特 に好ましくは 215°C以上であり、また、好ましくは 260°C以下、より好ましくは 255°C以 下、更に好ましくは 250°C以下、特に好ましくは 245°C以下である。 T50が前記下限 値未満であると、ディーゼル自動車における燃料消費率、エンジン出力、高温時の 始動性、アイドリング時のエンジンの回転の安定性が低下する傾向にある。他方、 T5 0が前記上限値を超えると、ディーゼル自動車にぉ 、てエンジン力も排出される粒子 状物質(Particle Matter,以下、 PMと!、う)が増加する傾向にある。  [0053] The 50% distillation temperature (hereinafter abbreviated as "T50") of the light oil composition according to the first embodiment is preferably 200 ° C or higher, more preferably 205 ° C or higher, and still more preferably. 210 ° C or higher, particularly preferably 215 ° C or higher, preferably 260 ° C or lower, more preferably 255 ° C or lower, still more preferably 250 ° C or lower, particularly preferably 245 ° C or lower. is there. If T50 is less than the lower limit, the fuel consumption rate, engine output, startability at high temperatures, and stability of engine rotation at idling tend to decrease in diesel vehicles. On the other hand, when T50 exceeds the above upper limit value, particulate matter (hereinafter referred to as PM!) That emits engine power tends to increase in diesel vehicles.
[0054] また、第 1実施形態に係る軽油組成物の 90%留出温度(以下、「T90」と略す。 )は 、好ましくは 265°C以上、より好ましくは 270°C以上、更に好ましくは 275°C以上、特 に好ましくは 280°C以上であり、また、好ましくは 335°C以下、より好ましくは 330°C以 下、更に好ましくは 325°C以下、特に好ましくは 320°C以下である。 T90が前記下限 値未満であると、ディーゼル自動車における燃料消費率、高温時の始動性、アイドリ ング時のエンジンの回転の安定性が低下する傾向にある。また、軽油組成物が低温 流動性向上剤を含有する場合には、低温流動性向上剤による目詰まり点等の改善 効果が低下する傾向にある。他方、 T90が前記上限値を超えると、ディーゼル自動 車にぉ 、てエンジン力 排出される PMが増加する傾向にある。  [0054] The 90% distillation temperature (hereinafter abbreviated as "T90") of the light oil composition according to the first embodiment is preferably 265 ° C or higher, more preferably 270 ° C or higher, and still more preferably. 275 ° C or higher, particularly preferably 280 ° C or higher, preferably 335 ° C or lower, more preferably 330 ° C or lower, further preferably 325 ° C or lower, particularly preferably 320 ° C or lower. is there. When T90 is less than the lower limit, the fuel consumption rate, startability at high temperatures, and stability of engine rotation at idling tend to decrease in diesel vehicles. Further, when the light oil composition contains a low temperature fluidity improver, the effect of improving the clogging point and the like by the low temperature fluidity improver tends to decrease. On the other hand, when T90 exceeds the upper limit, the PM discharged from the engine power tends to increase compared to the diesel motor.
[0055] また、第 1実施形態に係る軽油組成物の終点(以下、「EP」と略す。 )は、好ましくは 310°C以上、より好ましくは 315°C以上、更に好ましくは 320°C以上、特に好ましくは 325°C以上であり、また、好ましくは 355°C以下、より好ましくは 350°C以下、更に好 ましくは 345°C以下、特に好ましくは 340°C以下である。 EPが前記下限値未満であ ると、ディーゼル自動車における燃料消費率、高温時の始動性、アイドリング時のェ ンジンの回転の安定性が低下する傾向にある。また、軽油組成物が低温流動性向上 剤を含有する場合には、低温流動性向上剤による目詰まり点等の改善効果が低下 する傾向にある。他方、 EPが前記上限値を超えると、ディーゼル自動車においてェ ンジン力 排出される PMが増加する傾向にある。 [0055] The end point (hereinafter abbreviated as "EP") of the light oil composition according to the first embodiment is preferably 310 ° C or higher, more preferably 315 ° C or higher, further preferably 320 ° C or higher, particularly preferably 325 ° C or higher, preferably 355 ° C or lower, more preferably 350 ° C or lower, still more preferable. It is preferably 345 ° C or less, particularly preferably 340 ° C or less. If EP is less than the lower limit, the fuel consumption rate, startability at high temperatures, and engine rotation stability at idling tend to decrease in diesel vehicles. Further, when the light oil composition contains a low temperature fluidity improver, the improvement effect such as clogging point due to the low temperature fluidity improver tends to decrease. On the other hand, when EP exceeds the upper limit, PM emitted from engine power in diesel vehicles tends to increase.
[0056] なお、本発明で!/、う riBPj、「T10」、「Τ50」、「Τ90」及び「ΕΡ」とは、それぞれ JIS [0056] In the present invention,! /, U riBPj, "T10", "Τ50", "Τ90" and "ΕΡ" are JIS, respectively.
K 2254「石油製品 蒸留試験方法 常圧法」に準拠して測定される値を意味す る。  Means a value measured in accordance with K 2254 “Petroleum products distillation test method atmospheric pressure method”.
[0057] また、第 1実施形態に係る軽油組成物の潤滑性に関し、その HFRRの WS1. 4値 は、好ましくは 500以下、より好ましくは 460以下、更に好ましくは 420以下、得に好 ましくは 400以下である。 WS1. 4値が上記条件を満たすことで、ディーゼル自動車 における噴射ポンプ内の潤滑性を十分に確保することができる。なお、本発明でいう 「HFRRの WS1. 4値」とは、軽油の潤滑性の判断指標であり、社団法人石油学会か ら発行されて 、る石油学会規格 JPI— 5S— 50— 98「軽油 潤滑性試験方法」に準 拠して測定される値を意味する。  [0057] Regarding the lubricity of the light oil composition according to the first embodiment, the WS1.4 value of the HFRR is preferably 500 or less, more preferably 460 or less, and even more preferably 420 or less. Is less than 400. When the WS1.4 value satisfies the above conditions, sufficient lubricity can be secured in the injection pump of a diesel vehicle. The “HFRR WS1.4 value” in the present invention is an index for determining the lubricity of diesel oil. JPI-5S-50-98 “Diesel Oil” issued by the Japan Petroleum Institute It means the value measured according to the “Lubricity Test Method”.
[0058] (第 2実施形態)  [0058] (Second Embodiment)
本発明の第 2実施形態に係る軽油組成物は、下記条件 (A— 2)、 ^ 2)及び(じ - 2)を満たすことを特徴とする。  The light oil composition according to the second embodiment of the present invention is characterized by satisfying the following conditions (A-2), ^ 2), and (ji-2).
(A- 2)炭素数 10〜24のパラフィンの組成が下記式(1— 2)で表される条件を満す こと。  (A-2) The composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-2).
[数 7]  [Equation 7]
24  twenty four
370.0 < > /(«) < 430.0 (1 - 2)  370.0 <> / («) <430.0 (1-2)
[式(1— 2)中、 nはパラフィンの炭素数を示し、 f (n)は下記式(2): [In the formula (1-2), n represents the carbon number of paraffin, and f (n) represents the following formula (2):
[数 8] f(n) = 27.45 - 3,55( I a)― 0.65(c I a) (2) [Equation 8] f (n) = 27.45-3,55 (I a) ― 0.65 (c I a) (2)
(nは 10〜24の整数を示し、 a、 b及び cはそれぞれ炭素数 nのパラフィンの全量に占 める炭素数 nのノルマルパラフィン、炭素数 nの 1分岐のイソパラフィン及び炭素数 n の 2分岐以上のイソパラフィンの割合 (モル換算値)を示す。 ) (n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
で表される炭素数 nのパラフィン組成パラメータを示す。 ]  The paraffin composition parameter of carbon number n represented by these is shown. ]
(B— 2)留出温度 250°Cにおける留出量 E250が 5〜45%であること。  (B-2) Distillation amount E250 at a distillation temperature of 250 ° C is 5 to 45%.
(C 2)徐冷曇り点が 6. 0°C以下であること。  (C 2) Slow cooling cloud point is 6.0 ° C or less.
[0059] 上記条件 (A— 2)に関し、炭素数 10〜24の範囲における f (n)の合計 (上記式(1 —2)中の中辺)は、前述の通り 370. 0〜430. 0であり、好ましくは 375. 0〜410. 0 、より好ましくは 380. 0〜400. 0、更に好ましくは 382. 0〜390. 0である。炭素数 1 0〜24の範囲における f (n)の合計が 370. 0未満であると容量発熱量が低くなつて 容量あたりの燃費が大幅に低下してしまい、また、 430. 0を超えると粘度が増加して しま 、適切な噴射制御ができなくなる。  [0059] Regarding the above condition (A-2), the sum of f (n) in the range of 10 to 24 carbon atoms (the middle side in the above formula (1-2)) is 37.0 to 430. 0, preferably 375.0 to 410.0, more preferably 380.0 to 40.0, and still more preferably 383.0 to 390.0. If the sum of f (n) in the range of carbon numbers from 10 to 24 is less than 370.0, the calorific value of the capacity will be low and the fuel consumption per capacity will be greatly reduced. Viscosity will increase and proper jetting control will not be possible.
[0060] また、第 2実施形態に係る軽油組成物における芳香族分の含有量は特に制限され ないが、 PM等の生成を抑制する点から、組成物全量を基準として、好ましくは 15容 量%以下、より好ましくは 10容量%以下、更に好ましくは 5容量%以下、特に好ましく は 1容量%以下である。  [0060] The content of the aromatic component in the light oil composition according to the second embodiment is not particularly limited, but preferably 15 volumes based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. % Or less, more preferably 10% by volume or less, still more preferably 5% by volume or less, and particularly preferably 1% by volume or less.
[0061] また、第 2実施形態に係る軽油組成物におけるナフテン分の含有量は特に制限さ れないが、 PM等の生成を抑制する点から、組成物全量を基準として、好ましくは 30 容量%以下、より好ましくは 20容量%以下、更に好ましくは 15容量%以下、特に好 ましくは 10容量%以下である。  [0061] The naphthene content in the light oil composition according to the second embodiment is not particularly limited, but is preferably 30% by volume based on the total amount of the composition from the viewpoint of suppressing the production of PM and the like. Below, more preferably 20% by volume or less, still more preferably 15% by volume or less, and particularly preferably 10% by volume or less.
[0062] また、第 2実施形態に係る軽油組成物の硫黄分の含有量は、ディーゼル自動車の 排ガス後処理装置の浄ィ匕性能を良好に保持できることから、組成物全量を基準とし て、好ましくは 10質量 ppm以下であり、より好ましくは 5質量 ppm以下、より好ましくは 3質量 ppm以下、特に好ましくは 1質量 ppm以下である。  [0062] Further, the sulfur content of the light oil composition according to the second embodiment is preferably based on the total amount of the composition because the purification performance of the exhaust gas aftertreatment device of a diesel vehicle can be maintained satisfactorily. Is 10 mass ppm or less, more preferably 5 mass ppm or less, more preferably 3 mass ppm or less, and particularly preferably 1 mass ppm or less.
[0063] また、上記条件 (B— 2)に関し、第 2実施形態に係る軽油組成物の E250は、上述 の通り 5〜45%であることが必要であり、好ましくは 10〜43%、より好ましくは 15〜4 0%、更に好ましくは 17〜38%である。 E250が 5%未満であると、ディーゼル自動車 に使用されるゴム製部材の耐性が不十分となる。また、 E250が 45%を超えると、ディ ーゼル自動車における燃料消費率、エンジン出力、高温における始動性、アイドリン グ時のエンジンの回転の安定性などの性能を維持できなくなる。 [0063] Regarding the above condition (B-2), E250 of the light oil composition according to the second embodiment needs to be 5 to 45% as described above, and preferably 10 to 43%. Preferably it is 15-40%, More preferably, it is 17-38%. Diesel cars with E250 below 5% The resistance of the rubber member used for the is insufficient. If the E250 exceeds 45%, the fuel consumption rate, engine output, startability at high temperatures, and engine rotation stability during idling cannot be maintained.
[0064] また、上記条件 (C 2)に関し、第 2実施形態に係る軽油組成物の徐冷曇り点は、 前述の通り 6. 0°Cを超えることが必要であり、好ましくは 5. 5°C以上、より好まし くは 5. 2°C以上、更に好ましくは 5. 0°C以上である。徐冷曇り点が 6. 0°Cを超 えるようにすることで、低温流動性向上剤による目詰まり点降下能を十分に得ることが できる。なお、本発明でいう「徐冷曇り点」とは以下のようにして測定される値を意味す る。すなわち、底面がアルミニウム面である試料容器に厚さが 1. 5mmとなるように試 料を入れ、容器の底面より 3mmの高さから光を照射する。この状態で、曇り点よりも 1 0°C以上高い温度力 0. 5°CZ分で徐冷し、反射光の光量が照射光の 7Z8以下と なる温度 (徐冷曇り点)を 0. 1°C単位で検知する。  [0064] Regarding the condition (C2), the slow cooling cloud point of the light oil composition according to the second embodiment needs to exceed 6.0 ° C as described above, and preferably 5.5. It is at least ° C, more preferably at least 5.2 ° C, and even more preferably at least 5.0 ° C. By allowing the slow cooling cloud point to exceed 6.0 ° C, the clogging point lowering ability by the low temperature fluidity improver can be sufficiently obtained. The “slow cooling cloud point” in the present invention means a value measured as follows. In other words, put a sample in a sample container whose bottom is an aluminum surface so that the thickness is 1.5 mm, and irradiate light from a height of 3 mm from the bottom of the container. In this state, cool slowly at a temperature force of 0.5 ° CZ higher by 10 ° C or more than the cloud point, and set the temperature at which the amount of reflected light is 7Z8 or less of the irradiated light (slow cooling cloud point) to 0.1. Detect in ° C units.
[0065] 第 2実施形態に係る軽油組成物を構成する基材は、軽油組成物が上記条件 (A— 2)、(B—2)、(C— 2)を満たす限りにおいて特に制限されず、石油系軽油基材、石 油系灯油基材、合成系軽油基材及び合成系灯油基材のうちの 1種を単独で、または 2種以上を組み合わせて用いることができる。なお、 2種以上の基材を組み合わせて 用いる場合、各基材が単独で上記条件 (A— 2)、(B— 2)、(C— 2)を満たす必要は なぐそれらを混合した後の軽油組成物が上記条件 (A— 2)、(B— 2)、(C— 2)を満 たせばよい。  [0065] The base material constituting the light oil composition according to the second embodiment is not particularly limited as long as the light oil composition satisfies the above conditions (A-2), (B-2), and (C-2). In addition, one of petroleum-based light oil base, petroleum-based kerosene base, synthetic light-oil base and synthetic kerosene base can be used alone or in combination of two or more. When two or more types of base materials are used in combination, it is not necessary for each base material to satisfy the above conditions (A-2), (B-2), and (C-2). The light oil composition only needs to satisfy the above conditions (A-2), (B-2), and (C-2).
[0066] 第 2実施形態において用いられる石油系軽油基材、石油系灯油基材、合成系軽油 基材及び合成系灯油基材は、上記第 1実施形態の場合と同様であるため、ここでは 重複する説明を省略する。  [0066] The petroleum-based light oil base material, petroleum-based kerosene base material, synthetic-based light oil base material, and synthetic-based kerosene base material used in the second embodiment are the same as those in the first embodiment, so here A duplicate description is omitted.
[0067] 第 2実施形態に係る軽油組成物は、上記の石油系基材及び Z又は合成系基材の うちの 1種又は 2種以上を含有することができるが、それらの中でも、硫黄分や芳香族 分と 、つた環境負荷を増加させる頻度を低減する点から、合成系軽油基材及び Z又 は合成系灯油基材を必須成分として含有することが好ま ヽ。合成系軽油基材及び Z又は合成系灯油基材の含有量の合計は、組成物全量を基準として、 20容量%以 上であることが好ましぐ 30容量%以上であることがより好ましぐ 40容量%以上であ ることが更に好ましぐ 50容量%以上であることが特に好ましい。 [0067] The light oil composition according to the second embodiment may contain one or more of the above-mentioned petroleum-based substrates and Z or synthetic-based substrates, and among them, the sulfur content It is preferable to contain a synthetic light oil base material and a Z or synthetic kerosene base material as essential components from the viewpoint of reducing the frequency of increasing the environmental load, and aromatic components. The total content of the synthetic light oil base and the Z or synthetic kerosene base is preferably 20% by volume or more, more preferably 30% by volume or more, based on the total amount of the composition. 40% or more by volume More preferably, it is particularly preferably 50% by volume or more.
[0068] また、第 2実施形態に係る軽油組成物は上記の軽油基材及び Z又は灯油基材の みで構成されてもよいが、必要に応じて低温流動性向上剤を含有することができる。 低温流動性向上剤としては、上記第 1実施形態の説明において例示された低温流 動性向上剤と同様のものが使用可能である。低温流動性向上剤は 1種を単独で用い てもよく、または、 2種以上を組み合わせて使用してもよい。冷温流動性向上剤の中 でも汎用性の観点から、エチレン 酢酸ビニル共重合体系添加剤、極性窒素化合 物を含有する低温流動性向上剤を好ましく使用することができ、ワックス結晶微細化 促進および、ワックスの凝集沈降を防止する点で、極性窒素化合物を含有する低温 流動性向上剤の使用がさらに好ましい。 [0068] The light oil composition according to the second embodiment may be composed of only the light oil base and the Z or kerosene base, but may contain a low-temperature fluidity improver as necessary. it can. As the low temperature fluidity improver, the same low temperature fluidity improver as exemplified in the description of the first embodiment can be used. One low temperature fluidity improver may be used alone, or two or more low temperature fluidity improvers may be used in combination. Among the cold / temperature fluidity improvers, from the viewpoint of versatility, an ethylene-vinyl acetate copolymer additive and a low-temperature fluidity improver containing a polar nitrogen compound can be preferably used to promote wax crystal refinement and The use of a low-temperature fluidity improver containing a polar nitrogen compound is more preferred in terms of preventing wax aggregation and sedimentation.
[0069] 低温流動性向上剤の含有量は、組成物全量を基準として、好ましくは 50〜500mg ZL、より好ましくは 100〜300mgZLである。低温流動性向上剤の含有量が前記 下限値未満であると、その添カ卩による低温流動性向上効果が不十分となる傾向にあ る。また、低温流動性向上剤の含有量が前記上限値を超えても、含有量に見合う低 温流動性の更なる向上効果は得られな 、傾向にある。 [0069] The content of the low-temperature fluidity improver is preferably 50 to 500 mg ZL, more preferably 100 to 300 mg ZL, based on the total amount of the composition. If the content of the low temperature fluidity improver is less than the lower limit, the effect of improving the low temperature fluidity due to the additive tends to be insufficient. Further, even if the content of the low temperature fluidity improver exceeds the above upper limit, there is a tendency that a further improvement effect of the low temperature fluidity commensurate with the content cannot be obtained.
[0070] また、第 2実施形態に係る軽油組成物は、潤滑性向上剤を更に含有することができ る。潤滑性向上剤としては、上記第 1実施形態の説明において例示されたエステル 系、カルボン酸系、アルコール系、フエノール系、アミン系等の潤滑性向上剤の 1種 または 2種以上を使用することができる。この中でも、汎用性の観点から、エステル系 、カルボン酸系の潤滑性向上剤の使用が好ましい。さらに添加濃度に対する添加効 果が飽和に達しにくぐ HFRRの WS1. 4値をより小さくできる点からはエステル系潤 滑性向上剤が好ましぐ添加濃度に対する添加効果の初期応答性が高ぐ潤滑性向 上剤の添加量を少なくできる可能性があるという点からはカルボン酸系潤滑性向上 剤が好ましい。 [0070] Further, the light oil composition according to the second embodiment may further contain a lubricity improver. As the lubricity improver, one or more of the ester-based, carboxylic acid-based, alcohol-based, phenol-based, and amine-based lubricity improvers exemplified in the description of the first embodiment above should be used. Can do. Among these, from the viewpoint of versatility, it is preferable to use an ester-based or carboxylic acid-based lubricity improver. In addition, it is difficult for the additive effect to reach saturation. From the point that the WS1.4 value of HFRR can be made smaller, ester-type lubricity improvers are preferred. Carboxylic acid type lubricity improvers are preferred from the viewpoint that the amount of the improver added can be reduced.
[0071] 潤滑性向上剤の含有量は、組成物全量を基準として、好ましくは 25〜500mg/L 、より好ましくは 25〜300mgZL、更に好ましくは 25〜200mgZLである。潤滑性向 上剤の含有量が前記下限値未満であると、その添加による潤滑性向上効果が不十 分となる傾向にある。また、潤滑性向上剤の含有量が前記上限値を超えても、含有 量に見合う低温流動性の更なる向上効果は得られな 、傾向にある。 [0071] The content of the lubricity improver is preferably 25 to 500 mg / L, more preferably 25 to 300 mgZL, still more preferably 25 to 200 mgZL, based on the total amount of the composition. When the content of the lubricity improver is less than the lower limit, the effect of improving the lubricity due to the addition tends to be insufficient. Also, even if the content of the lubricity improver exceeds the upper limit, A further improvement effect of low-temperature fluidity commensurate with the amount tends to be obtained.
[0072] また、第 2実施形態に係る軽油組成物は、上記の低温流動性向上剤又は潤滑性 向上剤以外の添加剤を更に含有してもよい。力かる添加剤としては、アルケニルコハ ク酸誘導体、カルボン酸のアミン塩等の清浄剤、フエノール系、アミン系等の酸ィ匕防 止剤、サリチリデン誘導体等の金属不活性化剤、ポリダリコールエーテル等の氷結防 止剤、脂肪族ァミン、ァルケニルコハク酸エステル等の腐食防止剤、ァニオン系、力 チオン系、両性系界面活性剤等の帯電防止剤、ァゾ染料等の着色剤、シリコン系等 の消泡剤などを挙げることができる。これらの他の添加剤は、単独または数種類を組 み合わせて添加することができる。添加量も適宜選択することができる力 その他の 添加剤全量で、軽油組成物に対して、例えば、 0. 5質量%以下とすることができ、好 ましくは 0. 2質量%以下である。なお、ここでいう添カ卩量全量とは、添加剤の有効成 分としての添加量を意味して!/ヽる。  [0072] The light oil composition according to the second embodiment may further contain an additive other than the low-temperature fluidity improver or the lubricity improver. Examples of powerful additives include detergents such as alkenyl succinic acid derivatives, carboxylic acid amine salts, phenolic and amine-based acid detergents, metal deactivators such as salicylidene derivatives, and polydaricol. Anti-icing agents such as ether, corrosion inhibitors such as aliphatic amines, alkenyl succinates, anti-static agents such as anionic, force thione, and amphoteric surfactants, coloring agents such as azo dyes, silicones, etc. An antifoaming agent can be mentioned. These other additives can be added singly or in combination of several kinds. Power that can be selected as appropriate Addition amount Other additives Total amount can be, for example, 0.5% by mass or less, and preferably 0.2% by mass or less, with respect to the light oil composition. . Here, the total amount of the additive added means the added amount as an effective component of the additive!
[0073] 第 2実施形態に係る軽油組成物は、各種性能の更なる改善の点から、上記条件 (A — 2)、(B— 2)、(C— 2)に加えて、以下に示す条件を満たすことが好ましい。  [0073] In addition to the above conditions (A-2), (B-2), and (C-2), the light oil composition according to the second embodiment is shown below from the viewpoint of further improving various performances. It is preferable to satisfy the conditions.
[0074] 第 2実施形態に係る軽油組成物のセタン指数は、着火性の観点から、好ましくは 6 5以上であり、より好ましくは 70以上、更に好ましくは 75以上、特に好ましくは 80以上 である。  [0074] From the viewpoint of ignitability, the cetane index of the light oil composition according to the second embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 75 or more, and particularly preferably 80 or more. .
[0075] また、第 2実施形態に係る軽油組成物のセタン価は、着火性の観点から、好ましく は 65以上であり、より好ましくは 70以上、更に好ましくは 75以上、特に好ましくは 80 以上である。  [0075] Further, from the viewpoint of ignitability, the cetane number of the light oil composition according to the second embodiment is preferably 65 or more, more preferably 70 or more, still more preferably 75 or more, and particularly preferably 80 or more. is there.
[0076] また、上記条件 (C 2)に関し、第 2実施形態に係る軽油組成物の流動点は、好ま しくは 2. 5°C以下、より好ましくは 5. 0°C以下である。流動点を上記上限値以下 とすることで、ディーゼル自動車における燃料ラインでの流動性を十分に確保するこ とがでさる。  [0076] Regarding the condition (C2), the pour point of the light oil composition according to the second embodiment is preferably 2.5 ° C or less, more preferably 5.0 ° C or less. By setting the pour point below the above upper limit, sufficient fluidity in the fuel line of diesel vehicles can be secured.
[0077] また、第 2実施形態に係る軽油組成物の目詰まり点は、ディーゼル自動車の燃料 噴射装置に設けられるフィルターの閉塞を抑制できることから、好ましくは 1°C以下 であり、より好ましくは 2°C以下、更に好ましくは 3°C以下、特に好ましくは 4°C 以下である。 [0078] また、第 2実施形態に係る軽油組成物の 30°Cにおける動粘度は、好ましくは 2. Om m2Zs以上、より好ましくは 2. 2mm2Zs以上、更に好ましくは 2. 4mm2Zs以上、特 に好ましくは 2. 5mm2Zs以上であり、また、好ましくは 4. 2mm2Zs以下、より好まし くは 4. 0mm2Zs以下、更に好ましくは 3. 9mm2Zs以下、特に好ましくは 3. 8mm2 Zs以下である。 30°Cにおける動粘度が前記下限値未満であると、ディーゼル自動 車において比較的高い温度下で使用された場合に、始動不良が起こりやすくなり、 また、アイドリング時のエンジンの回転が不安定ィ匕する傾向にある。他方、 30°Cにお ける動粘度が前記上限値を超えると、排ガス中の黒煙量が増大する傾向にある。 [0077] Further, the clogging point of the light oil composition according to the second embodiment is preferably 1 ° C or less, more preferably 2 because it can suppress the clogging of the filter provided in the fuel injection device of the diesel vehicle. ° C or lower, more preferably 3 ° C or lower, particularly preferably 4 ° C or lower. [0078] The kinematic viscosity at 30 ° C of the light oil composition according to the second embodiment is preferably 2. Om m 2 Zs or more, more preferably 2.2 mm 2 Zs or more, and further preferably 2.4 mm 2. Zs above, preferably especially 2 is a 5 mm 2 Zs or more, and preferably 4. 2 mm 2 Zs less, more rather preferably is 4. 0 mm 2 Zs less, more preferably 3. 9 mm 2 Zs less, particularly Preferably it is 3.8 mm 2 Zs or less. If the kinematic viscosity at 30 ° C is less than the above lower limit value, start-up failure is likely to occur when the diesel vehicle is used at a relatively high temperature, and engine rotation during idling is unstable. Tends to hesitate. On the other hand, when the kinematic viscosity at 30 ° C exceeds the upper limit, the amount of black smoke in the exhaust gas tends to increase.
[0079] また、第 2実施形態に係る軽油組成物の引火点は、取り扱い時の安全性の点から、 好ましくは 60°C以上であり、より好ましくは 65°C以上、更に好ましくは 70°C以上、特 に好ましくは 75°C以上である。  [0079] The flash point of the light oil composition according to the second embodiment is preferably 60 ° C or higher, more preferably 65 ° C or higher, and still more preferably 70 °, from the viewpoint of safety during handling. C or higher, particularly preferably 75 ° C or higher.
[0080] また、第 2実施形態に係る軽油組成物の蒸留性状に関し、その初留点 (IBP)は、 好ましくは 155°C以上、より好ましくは 160°C以上、更に好ましくは 165°C以上、特に 好ましくは 170°C以上であり、また、好ましくは 225°C以下、より好ましくは 220°C以下 、更に好ましくは 215°C以下、特に好ましくは 210°C以下である。 IBPが前記下限値 未満であると、一部の軽質留分が気化し、ディーゼル自動車のエンジン内において 噴霧範囲が広範囲となることに伴って排出ガス中の未燃の炭化水素量が増大し、そ の結果、高温時の始動性及びアイドリング時のエンジンの回転の安定性が低下する 傾向にある。他方、 IBPが前記上限値を超えると、ディーゼル自動車における低温時 の始動性及び運転性が低下する傾向にある。  [0080] Further, regarding the distillation properties of the light oil composition according to the second embodiment, the initial boiling point (IBP) is preferably 155 ° C or higher, more preferably 160 ° C or higher, and further preferably 165 ° C or higher. In particular, it is 170 ° C or higher, preferably 225 ° C or lower, more preferably 220 ° C or lower, further preferably 215 ° C or lower, particularly preferably 210 ° C or lower. If the IBP is less than the lower limit, a part of the light fraction is vaporized, and the amount of unburned hydrocarbons in the exhaust gas increases as the spray range becomes wider in the diesel engine. As a result, the startability at high temperatures and the stability of engine rotation at idling tend to decrease. On the other hand, if the IBP exceeds the upper limit, the startability and drivability at low temperatures in a diesel vehicle tend to deteriorate.
[0081] また、第 2実施形態に係る軽油組成物の 10%留出温度 (T10)は、好ましくは 175 °C以上、より好ましくは 180°C以上、更に好ましくは 185°C以上、特に好ましくは 190 °C以上であり、また、好ましくは 270°C以下、より好ましくは 265°C以下、更に好ましく は 260°C以下、特に好ましくは 255°C以下である。 T10が前記下限値未満であると、 一部の軽質留分が気化し、ディーゼル自動車のエンジン内において噴霧範囲が広 範囲となることに伴って排出ガス中の未年の炭化水素量が増大し、その結果、高温 時の始動性及びアイドリング時のエンジンの回転の安定性が低下する傾向にある。 他方、 T10が前記上限値を超えると、ディーゼル自動車における低温時の始動性及 び運転性が低下する傾向にある。 [0081] The 10% distillation temperature (T10) of the light oil composition according to the second embodiment is preferably 175 ° C or higher, more preferably 180 ° C or higher, still more preferably 185 ° C or higher, particularly preferably. Is 190 ° C or higher, preferably 270 ° C or lower, more preferably 265 ° C or lower, still more preferably 260 ° C or lower, particularly preferably 255 ° C or lower. If T10 is less than the lower limit, some light fractions are vaporized, and the amount of hydrocarbons in the exhaust gas increases as the spray range becomes wider in the diesel engine. As a result, startability at high temperatures and engine rotation stability at idling tend to be reduced. On the other hand, if T10 exceeds the upper limit, the startability at low temperatures in diesel vehicles and And drivability tends to decrease.
[0082] また、第 2実施形態に係る軽油組成物の 50%留出温度 (T50)は、好ましくは 230 °C以上、より好ましくは 235°C以上、更に好ましくは 240°C以上、特に好ましくは 245 °C以上であり、また、好ましくは 300°C以下、より好ましくは 295°C以下、更に好ましく は 290°C以下、特に好ましくは 285°C以下である。 T50が前記下限値未満であると、 ディーゼル自動車における燃料消費率、エンジン出力、高温時の始動性、アイドリン グ時のエンジンの回転の安定性が低下する傾向にある。他方、 T50が前記上限値を 超えると、ディーゼル自動車においてエンジン力 排出される粒子状物質 (PM)が増 加する傾向にある。  [0082] Further, the 50% distillation temperature (T50) of the light oil composition according to the second embodiment is preferably 230 ° C or higher, more preferably 235 ° C or higher, still more preferably 240 ° C or higher, particularly preferably. Is 245 ° C or higher, preferably 300 ° C or lower, more preferably 295 ° C or lower, still more preferably 290 ° C or lower, particularly preferably 285 ° C or lower. When T50 is less than the lower limit, the fuel consumption rate, engine output, startability at high temperatures, and engine rotation stability at idling tend to be reduced in diesel vehicles. On the other hand, when T50 exceeds the upper limit, particulate matter (PM) discharged from the engine power of diesel vehicles tends to increase.
[0083] また、第 2実施形態に係る軽油組成物の 90%留出温度 (T90)は、好ましくは 285 °C以上、より好ましくは 290°C以上、更に好ましくは 295°C以上、特に好ましくは 300 °C以上であり、また、好ましくは 335°C以下、より好ましくは 330°C以下、更に好ましく は 325°C以下、特に好ましくは 320°C以下である。 T90が前記下限値未満であると、 ディーゼル自動車における燃料消費率、高温時の始動性、アイドリング時のエンジン の回転の安定性が低下する傾向にある。また、軽油組成物が低温流動性向上剤を 含有する場合には、低温流動性向上剤による目詰まり点等の改善効果が低下する 傾向にある。他方、 T90が前記上限値を超えると、ディーゼル自動車においてェンジ ンカも排出される PMが増加する傾向にある。  [0083] The 90% distillation temperature (T90) of the light oil composition according to the second embodiment is preferably 285 ° C or higher, more preferably 290 ° C or higher, still more preferably 295 ° C or higher, particularly preferably. Is not lower than 300 ° C, preferably not higher than 335 ° C, more preferably not higher than 330 ° C, still more preferably not higher than 325 ° C, particularly preferably not higher than 320 ° C. If T90 is less than the lower limit, the fuel consumption rate, startability at high temperatures, and engine rotation stability at idling tend to decrease in diesel vehicles. Further, when the light oil composition contains a low temperature fluidity improver, the improvement effect such as clogging point by the low temperature fluidity improver tends to decrease. On the other hand, when T90 exceeds the upper limit, the PM emitted by the engine in a diesel vehicle tends to increase.
[0084] また、第 2実施形態に係る軽油組成物の終点 (EP)は、好ましくは 305°C以上、より 好ましくは 310°C以上、更に好ましくは 315°C以上、特に好ましくは 320°C以上であり 、また、好ましくは 355°C以下、より好ましくは 350°C以下、更に好ましくは 345°C以 下、特に好ましくは 340°C以下である。 EPが前記下限値未満であると、ディーゼル自 動車における燃料消費率、高温時の始動性、アイドリング時のエンジンの回転の安 定性が低下する傾向にある。また、軽油組成物が低温流動性向上剤を含有する場 合には、低温流動性向上剤による目詰まり点等の改善効果が低下する傾向にある。 他方、 EPが前記上限値を超えると、ディーゼル自動車においてエンジン力 排出さ れる PMが増加する傾向にある。  [0084] The end point (EP) of the light oil composition according to the second embodiment is preferably 305 ° C or higher, more preferably 310 ° C or higher, still more preferably 315 ° C or higher, and particularly preferably 320 ° C. Further, it is preferably 355 ° C or lower, more preferably 350 ° C or lower, further preferably 345 ° C or lower, and particularly preferably 340 ° C or lower. If EP is less than the lower limit, the fuel consumption rate, startability at high temperatures, and stability of engine rotation at idling tend to decrease in diesel vehicles. Further, when the light oil composition contains a low temperature fluidity improver, the improvement effect such as a clogging point due to the low temperature fluidity improver tends to decrease. On the other hand, when EP exceeds the upper limit, PM discharged from the engine power of diesel vehicles tends to increase.
[0085] また、第 2実施形態に係る軽油組成物の潤滑性に関し、その HFRRの WS 1. 4値 は、好ましくは 500以下、より好ましくは 460以下、更に好ましくは 420以下、得に好 ましくは 400以下である。 WS1. 4値が上記条件を満たすことで、ディーゼル自動車 における噴射ポンプ内の潤滑性を十分に確保することができる。 [0085] Further, regarding the lubricity of the light oil composition according to the second embodiment, WS 1.4 value of HFRR. Is preferably 500 or less, more preferably 460 or less, still more preferably 420 or less, and particularly preferably 400 or less. When the WS1.4 value satisfies the above conditions, sufficient lubricity can be secured in the injection pump of a diesel vehicle.
実施例  Example
[0086] 以下、実施例及び比較例に基づき本発明を更に具体的に説明するが、本発明は 以下の実施例に何ら限定されるものではない。  [0086] Hereinafter, the present invention will be more specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
[0087] [実施例 1〜2、比較例 1〜3]  [0087] [Examples 1-2, Comparative Examples 1-3]
実施例 1〜2及び比較例 1〜3にお ヽては、それぞれ表 1に示す組成及び性状を有 する軽油組成物を用意した。実施例 1〜2の軽油組成物はそれぞれ、フィッシャー'ト 口プシュ反応により天然ガス力 ワックス及び中間留分を得、これに水素化処理を施 して得られた燃料である。比較例 1の軽油組成物は、一般的な水素化精製により製 造された原油由来の燃料である。比較例 2の軽油組成物は、フィッシャー 'トロプシュ 反応により天然ガスからワックス及び中間留分を得、これに水素化処理を施して得ら れた燃料である力 実施例 1〜2の軽油組成物に比べて水素化処理の度合!/、を低く した燃料である。比較例 3の軽油組成物は、一般的な水素化精製により製造された 原油由来の燃料に更に水素化処理を施し、更なる低硫黄化及び低芳香族化を図つ た燃料である。  For Examples 1-2 and Comparative Examples 1-3, light oil compositions having the compositions and properties shown in Table 1 were prepared. Each of the light oil compositions of Examples 1 and 2 is a fuel obtained by obtaining a natural gas power wax and a middle distillate by a Fischer's mouth push reaction and subjecting them to hydrogenation treatment. The diesel oil composition of Comparative Example 1 is a crude oil-derived fuel produced by general hydrorefining. The light oil composition of Comparative Example 2 is a fuel obtained by obtaining a wax and middle distillate from natural gas by the Fischer's Tropsch reaction and hydrotreating it. The light oil composition of Examples 1 and 2 This is a fuel with a lower degree of hydrotreatment! The diesel oil composition of Comparative Example 3 is a fuel in which crude oil-derived fuel produced by general hydrorefining is further hydrotreated to further reduce sulfur and aroma.
[0088] 次に、実施例 1〜2及び比較例 1〜3の各軽油組成物について以下の試験を実施 した。  [0088] Next, the following tests were performed on the light oil compositions of Examples 1-2 and Comparative Examples 1-3.
[0089] [着火性試験]  [0089] [Ignition test]
低温時の着火性を確認するために、環境温度の制御が可能なシャーシダイナモメ ータ上で、下記のディーゼル次号者を用いて低温時の白煙の測定を行った。  In order to check the ignitability at low temperatures, white smoke at low temperatures was measured on a chassis dynamometer capable of controlling the environmental temperature using the following diesel engineer.
(車両諸元)  (Vehicle specifications)
エンジン種類:インタークーラー付き過給直列 4気筒ディーゼル  Engine type: Supercharged inline 4-cylinder diesel with intercooler
排気量: 3L  Displacement: 3L
圧縮比: 18. 5  Compression ratio: 18.5
最高出力: 125kWZ3400rpm  Maximum output: 125kWZ3400rpm
最高トルク: 350NmZ2400rpm 規制適合:平成 9年度排ガス規制適合 Maximum torque: 350NmZ2400rpm Compliance with regulations: 1997 exhaust gas regulations
ミッション: 4AT  Mission: 4AT
排ガス後処理装置:酸化触媒。  Exhaust gas aftertreatment device: oxidation catalyst.
[0090] 低温実車試験にお!ヽては、まず、室温下、ディーゼル自動車の燃料系統を評価燃 料 (各軽油組成物)でフラッシングした。フラッシング燃料を抜き出し、メインフィルタを 新品に交換した後、燃料タンクに評価燃料の規定量 (供試車両の燃料タンクの容量 の 1Z2)の張り込みを行った。その後、環境温度を室温から 5°Cまで急冷し、 5°Cで 1 時間保持した後、 l°CZhの冷却速度で— 10°Cに達するまで徐冷し、— 10°Cで 1時 間保持した後で走行試験を開始した。 10秒間のクランキングを 30秒間隔で 2回繰り 返しても始動しない場合は測定不能とした。また、始動できる場合は、アイドリングで 3 0秒間放置し、その後 5秒間でアクセルペダルを一杯まで踏み込む操作を 5回繰り返 し、その際の白煙量を透過型測定器で計測した。各軽油組成物について、 5回の平 均値を算出し、比較例 3の平均値を 100としたときの相対値を求め、着火性を評価し た。得られた結果を表 1に示す。  [0090] In the low-temperature actual vehicle test! First, the fuel system of the diesel vehicle was flushed with the evaluation fuel (each diesel oil composition) at room temperature. After extracting the flushing fuel and replacing the main filter with a new one, the specified amount of fuel to be evaluated (1Z2 of the fuel tank capacity of the test vehicle) was applied to the fuel tank. Then, rapidly cool the ambient temperature from room temperature to 5 ° C, hold it at 5 ° C for 1 hour, slowly cool it down to −10 ° C at a cooling rate of l ° CZh, and keep it at −10 ° C for 1 hour. After holding, the running test was started. Measurement was not possible if the 10-second cranking did not start after repeated twice at 30-second intervals. When the engine could be started, it was left for 30 seconds at idling, and then the operation of depressing the accelerator pedal to the full for 5 seconds was repeated 5 times, and the amount of white smoke at that time was measured with a transmission type measuring instrument. For each light oil composition, the average value of 5 times was calculated, and the relative value when the average value of Comparative Example 3 was taken as 100 was determined to evaluate the ignitability. The results obtained are shown in Table 1.
[0091] [低温実車試験]  [0091] [Low-temperature vehicle test]
環境温度の制御が可能なシャーシダイナモメータ上で、下記の A、 Bの 2台のディ ーゼル自動車を用いて低温実車試験を実施した。  On a chassis dynamometer capable of controlling the ambient temperature, a low-temperature vehicle test was conducted using the following two diesel vehicles, A and B.
(車両 A諸元)  (Vehicle A specifications)
最大積載量: 2t  Maximum loading capacity: 2t
エンジンの種類:直列 4気筒ディーゼル  Engine type: Inline 4-cylinder diesel
エンジンの総排気量: 4. 3L  Total engine displacement: 4.3L
燃料噴射ポンプ:列型  Fuel injection pump: row type
適合規格:短期排出ガス規制適合 (ベース車両)  Applicable standards: Compliant with short-term emission regulations (base vehicle)
排出ガス後処理装置:東京都指定の PM減少装置 (カテゴリー 4適合)  Exhaust gas aftertreatment device: PM reduction device designated by Tokyo (Category 4 compliant)
PM減少装置の使用燃料:低硫黄軽油 (硫黄分 50質量 ppm以下)。  Fuel used in PM reduction equipment: Low sulfur gas oil (sulfur content 50 mass ppm or less).
(車両 B諸元)  (Vehicle B specifications)
エンジンの種類:インタークーラー付き過給直列 4気筒ディーゼル  Engine type: Supercharged inline 4-cylinder diesel with intercooler
エンジンの総排気量: 3. OL 燃料噴射システム:コモンレール方式 Total engine displacement: 3. OL Fuel injection system: Common rail system
適合規格:長期排出ガス規制適合  Applicable standards: long-term emission regulations
排出ガス後処理装置:酸化触媒。  Exhaust gas aftertreatment device: oxidation catalyst.
[0092] 低温実車試験にお!ヽては、まず、室温下、ディーゼル自動車の燃料系統を評価燃 料 (各軽油組成物)でフラッシングした。フラッシング燃料を抜き出し、メインフィルタを 新品に交換した後、燃料タンクに評価燃料の規定量 (供試車両の燃料タンクの容量 の 1Z2)の張り込みを行った。その後、環境温度を室温から 5°Cまで急冷し、 5°Cで 1 時間保持した後、 l°CZhの冷却速度で— 10°Cに達するまで徐冷し、— 10°Cで 1時 間保持した後で走行試験を開始した。走行試験は、「エンジン始動」、「5分間アイドリ ング」、「50kmZhまで加速」及び「50kmZhで 1時間走行」で構成され、その巻の 運転状況により合否を判定した。具体的には、エンジン始動、アイドリング及び加速 に問題がなぐ前走行にわたって 50kmZhでの走行が維持できた場合を良(S)とし た。また、一回目のクランキングではエンジンが始動できな力つた場合、並びに走行 中一時的に車速が低下したがその後回復した場合など、軽微の不具合を生じたが、 走行が継続できた場合を可 (A)とした。また、始動不可(10秒間のクランキングを 30 秒間隔で 5回繰り返しても始動しない)、アイドリングストール、エンジン停止などにより 走行維持ができな力つた場合を不可 (B)とした。得られた結果を表 1に示す。  [0092] In the low-temperature actual vehicle test! First, the fuel system of a diesel vehicle was flushed with an evaluation fuel (each light oil composition) at room temperature. After extracting the flushing fuel and replacing the main filter with a new one, the specified amount of fuel to be evaluated (1Z2 of the fuel tank capacity of the test vehicle) was applied to the fuel tank. Then, rapidly cool the ambient temperature from room temperature to 5 ° C, hold it at 5 ° C for 1 hour, slowly cool it down to −10 ° C at a cooling rate of l ° CZh, and keep it at −10 ° C for 1 hour. After holding, the running test was started. The driving test consisted of “engine start”, “5 minutes idling”, “acceleration to 50 kmZh” and “running for 1 hour at 50 kmZh”, and the pass / fail was judged by the operating condition of the winding. Specifically, it was judged as good (S) when the vehicle was able to maintain 50kmZh over the previous run without any problems in engine start, idling and acceleration. In the first cranking, minor problems may have occurred, such as when the engine is strong enough to start but also when the vehicle's speed has dropped temporarily and then recovered. (A). In addition, it was determined to be impossible (B) when it was impossible to start (during 10 seconds of cranking, it would not start even if it was repeated 5 times at 30-second intervals), and when it was unable to keep running due to idling stall or engine stop. The results obtained are shown in Table 1.
[0093] [燃費試験]  [0093] [Fuel consumption test]
下記に示すディーゼルエンジン搭載車両を用いて、燃費の測定を行った。試験モ ードは、図 2に示す実走行を模擬した過渡運転モードで行い、燃費は試験モード中 に消費した燃料容積流量を燃料温度補正し、重量値に置き換えた値について、比較 例 1の燃料を供試した場合の結果を 100として、各結果を相対的に比較、定量化し た。  Fuel consumption was measured using a vehicle equipped with a diesel engine shown below. The test mode is performed in the transient operation mode that simulates the actual driving shown in Fig. 2, and the fuel consumption is corrected by comparing the fuel volume flow rate consumed during the test mode with the fuel temperature and replaced with the weight value. Each result was relatively compared and quantified, with the result when the fuel was tested as 100.
(車両諸元)  (Vehicle specifications)
エンジン種類:インタークーラー付過給直列 4気筒ディ ゼル  Engine type: Supercharged inline 4 cylinder with intercooler
エンジン総排気量: 3L  Engine displacement: 3L
圧縮比: 18. 5  Compression ratio: 18.5
最高出力: 125kWZ3400rpm 最高トルク: 350NmZ2400rpm Maximum output: 125kWZ3400rpm Maximum torque: 350NmZ2400rpm
規制適合:平成 9年度排ガス規制適合  Compliance with regulations: 1997 exhaust gas regulations
ミッション: 4AT  Mission: 4AT
排ガス後処理装置:酸化触媒。  Exhaust gas aftertreatment device: oxidation catalyst.
[0094] [表 1] [0094] [Table 1]
Figure imgf000027_0001
Figure imgf000027_0001
[0095] [実施例 3〜4、比較例 4〜6」 [Examples 3 to 4, Comparative Examples 4 to 6]
実施例 3〜4及び比較例 4〜6にお ヽては、それぞれ表 2に示す組成及び性状を有 する軽油組成物を用意した。実施例 3〜4の軽油組成物はそれぞれ、フィッシャー'ト 口プシュ反応により天然ガス力 ワックス及び中間留分を得、これに水素化処理を施 して得られた燃料である。比較例 4の軽油組成物は、一般的な水素化精製により製 造された原油由来の燃料である。比較例 5の軽油組成物は、フィッシャー 'トロプシュ 反応により天然ガスからワックス及び中間留分を得、これに水素化処理を施して得ら れた燃料である力 実施例 3〜4の軽油組成物に比べて水素化処理の度合 、を低く した燃料である。比較例 6の軽油組成物は、一般的な水素化精製により製造された 原油由来の燃料に更に水素化処理を施し、更なる低硫黄化及び低芳香族化を図つ た燃料である。 For Examples 3 to 4 and Comparative Examples 4 to 6, light oil compositions having the compositions and properties shown in Table 2 were prepared. Each of the light oil compositions of Examples 3 to 4 is a fuel obtained by obtaining a natural gas power wax and a middle distillate by a Fischer's mouth push reaction and subjecting them to a hydrotreatment. The diesel oil composition of Comparative Example 4 is a crude oil-derived fuel produced by general hydrorefining. The gas oil composition of Comparative Example 5 was obtained by obtaining wax and middle distillate from natural gas by Fischer's Tropsch reaction and subjecting it to hydrogenation treatment. This is a fuel with a reduced degree of hydrotreatment compared to the light oil compositions of Examples 3-4. The diesel oil composition of Comparative Example 6 is a fuel in which crude oil-derived fuel produced by general hydrorefining is further hydrotreated to further reduce sulfur and aroma.
[0096] 次に、実施例 3〜4及び比較例 4〜6の各軽油組成物について以下の試験を実施 した。  [0096] Next, the following tests were performed on the light oil compositions of Examples 3 to 4 and Comparative Examples 4 to 6.
[0097] [着火性試験]  [0097] [Ignition test]
低温時の着火性を確認するために、環境温度の制御が可能なシャーシダイナモメ ータ上で、下記のディーゼル次号者を用いて低温時の白煙の測定を行った。  In order to check the ignitability at low temperatures, white smoke at low temperatures was measured on a chassis dynamometer capable of controlling the environmental temperature using the following diesel engineer.
(車両諸元)  (Vehicle specifications)
エンジン種類:インタークーラー付き過給直列 4気筒ディーゼル  Engine type: Supercharged inline 4-cylinder diesel with intercooler
排気量: 3L  Displacement: 3L
圧縮比: 18. 5  Compression ratio: 18.5
最高出力: 125kWZ3400rpm  Maximum output: 125kWZ3400rpm
最高トルク: 350NmZ2400rpm  Maximum torque: 350NmZ2400rpm
規制適合:平成 9年度排ガス規制適合  Compliance with regulations: 1997 exhaust gas regulations
ミッション: 4AT  Mission: 4AT
排ガス後処理装置:酸化触媒。  Exhaust gas aftertreatment device: oxidation catalyst.
[0098] 低温実車試験にお!ヽては、まず、室温下、ディーゼル自動車の燃料系統を評価燃 料 (各軽油組成物)でフラッシングした。フラッシング燃料を抜き出し、メインフィルタを 新品に交換した後、燃料タンクに評価燃料の規定量 (供試車両の燃料タンクの容量 の 1Z2)の張り込みを行った。その後、環境温度を室温から 10°Cまで急冷し、 10°C で 1時間保持した後、 l°CZhの冷却速度で 0°Cに達するまで徐冷し、 0°Cで 1時間保 持した後で走行試験を開始した。 10秒間のクランキングを 30秒間隔で 2回繰り返し ても始動しない場合は測定不能とした。また、始動できる場合は、アイドリングで 30秒 間放置し、その後 5秒間でアクセルペダルを一杯まで踏み込む操作を 5回繰り返し、 その際の白煙量を透過型測定器で計測した。各軽油組成物について、 5回の平均 値を算出し、比較例 6の平均値を 100としたときの相対値を求め、着火性を評価した 。得られた結果を表 2に示す。 [0098] In the low-temperature actual vehicle test, first, the fuel system of the diesel vehicle was flushed with the evaluation fuel (each light oil composition) at room temperature. After extracting the flushing fuel and replacing the main filter with a new one, the specified amount of fuel to be evaluated (1Z2 of the fuel tank capacity of the test vehicle) was applied to the fuel tank. After that, the ambient temperature was rapidly cooled from room temperature to 10 ° C, held at 10 ° C for 1 hour, slowly cooled to 0 ° C at a cooling rate of l ° CZh, and kept at 0 ° C for 1 hour. Later, a running test was started. Measurement was not possible if the 10-second cranking did not start after repeated twice at 30-second intervals. When the engine could be started, it was left for 30 seconds by idling, and then the operation of depressing the accelerator pedal to the full for 5 seconds was repeated 5 times, and the amount of white smoke at that time was measured with a transmission type measuring instrument. For each light oil composition, the average value of 5 times was calculated, and the relative value when the average value of Comparative Example 6 was taken as 100 was determined, and the ignitability was evaluated. . Table 2 shows the results obtained.
[0099] [高温始動性試験] [0099] [High temperature startability test]
各軽油組成物の高温始動性を評価するため、環境温度及び湿度の制御が可能な シャーシダイナモメータ上で、下記のディーゼルエンジン搭載車両を用いて、以下の 手順に従って高温始動性試験を実施した。車両に供試燃料を 15L給油し、その後ェ ンジンを始動させてアイドリングにて保持した。環境温度を 25°Cに設定して試験室内 温度を安定させ、アイドリング中の車両の燃料噴射ポンプ出口温度が安定した時点 でエンジンを停止させた。エンジンの停止から 5分間放置した後、エンジンを再始動 させ、エンジンが正常に始動した場合は、環境温度を 30°C、 35°Cの順で上昇させて 前述の試験操作を繰り返した。上記試験において、正常に始動した場合を合格 (A) 、始動しなかった場合を不合格 (B)とした。得られた結果を表 2に示す。  In order to evaluate the high temperature startability of each diesel oil composition, a high temperature startability test was carried out according to the following procedure on a chassis dynamometer capable of controlling environmental temperature and humidity using the following diesel engine equipped vehicle. The vehicle was refueled with 15 L of the test fuel, and then the engine was started and held by idling. The ambient temperature was set to 25 ° C to stabilize the test room temperature, and the engine was stopped when the fuel injection pump outlet temperature of the idling vehicle was stabilized. After leaving the engine for 5 minutes, the engine was restarted and when the engine started normally, the environmental temperature was raised in the order of 30 ° C and 35 ° C, and the above test operation was repeated. In the above test, the case where the engine was started normally was regarded as acceptable (A), and the case where it was not activated was regarded as unacceptable (B). Table 2 shows the results obtained.
(車両諸元)  (Vehicle specifications)
最大積載量: 4t  Maximum loading capacity: 4t
エンジンの種類:直列 6気筒ディーゼル  Engine type: Inline 6-cylinder diesel
エンジンの総排気量: 8. 2L  Engine displacement: 8. 2L
燃料噴射ポンプ:高圧分配型  Fuel injection pump: High pressure distribution type
適合規格:長期排出ガス規制適合 (七都府県指定低公害車)  Applicable standards: Long-term emission regulations (Low pollution vehicles designated by seven prefectures)
排出ガス後処理装置:酸化触媒。  Exhaust gas aftertreatment device: oxidation catalyst.
[0100] [ゴム膨潤試験] [0100] [Rubber swelling test]
エンジン部品の O—リング等で使用されているゴム製部材に対する影響を確認する ため、以下に示す手順で浸せき試験を行った。ゴムを構成している化合物の 1つであ るアクリロニトリルが結合アクリロニトリル質量中心値として、全体の 25%以上 35%以 下である-トリルゴム(中-トリルゴム)を評価対象のゴム部材とし、 MIL R6855に準 拠して試験燃料を 100°Cに加熱、保持し、その中に試験ゴム部材を 70時間浸せきさ せた。 70時間後の試験ゴム部材の体積変化を測定し、ゴム製部材の耐性を評価した 。得られた結果を表 2に示す。表 1の「ゴム膨潤試験」の欄中、「A」は試験前後におけ る体積、硬さ、引っ張り強度のそれぞれの変化割合が ± 10%以内であったことを、「 B」は ± 10%〜士 20%であったことを、「C」は ± 20%以上であったことを、それぞれ 意味する。 In order to confirm the effect on the rubber parts used in the O-rings of engine parts, a soaking test was conducted according to the following procedure. One of the compounds that make up rubber is acrylonitrile, which has a combined acrylonitrile mass center value of 25% or more and 35% or less of the total. The test fuel was heated to 100 ° C and held in accordance with the test, and the test rubber member was immersed in it for 70 hours. The volume change of the test rubber member after 70 hours was measured to evaluate the resistance of the rubber member. Table 2 shows the results obtained. In the column of “Rubber Swelling Test” in Table 1, “A” indicates that the change rate of volume, hardness, and tensile strength before and after the test was within ± 10%, and “B” indicates ± 10%. % ~ Shi 20%, "C" was ± 20% or more, respectively means.
[0101] [燃費試験]  [0101] [Fuel consumption test]
下記に示すディーゼルエンジン搭載車両を用いて、燃費の測定を行った。試験モ ードは、図 2に示す実走行を模擬した過渡運転モードで行い、燃費は試験モード中 に消費した燃料容積流量を燃料温度補正し、重量値に置き換えた値について、比較 例 4の燃料を供試した場合の結果を 100として、各結果を相対的に比較、定量化し た。得られた結果を表 2に示す。  Fuel consumption was measured using a vehicle equipped with a diesel engine shown below. The test mode is performed in the transient operation mode that simulates the actual driving shown in Fig. 2, and the fuel efficiency is the value obtained by correcting the fuel volume flow consumed during the test mode with the fuel temperature and replacing it with the weight value. Each result was relatively compared and quantified, with the result when the fuel was tested as 100. Table 2 shows the results obtained.
(車両諸元)  (Vehicle specifications)
エンジン種類:インタークーラー付過給直列 4気筒ディ ゼル  Engine type: Supercharged inline 4 cylinder with intercooler
エンジン総排気量: 3L  Engine displacement: 3L
圧縮比: 18. 5  Compression ratio: 18.5
最高出力: 125kWZ3400rpm  Maximum output: 125kWZ3400rpm
最高トルク: 350NmZ2400rpm  Maximum torque: 350NmZ2400rpm
規制適合:平成 9年度排ガス規制適合  Compliance with regulations: 1997 exhaust gas regulations
ミッション: 4AT  Mission: 4AT
排ガス後処理装置:酸化触媒。  Exhaust gas aftertreatment device: oxidation catalyst.
[0102] [表 2] [0102] [Table 2]
実施例 実施例 比較例 比較例 比較例 3 4 4 5 6 Examples Examples Comparative Examples Comparative Examples Comparative Examples 3 4 4 5 6
∑/(") 387.6 384.9 364.2 352.7 382.2 硫黄分(質量 ppm) <1 <1 5 <1 <1 芳香族分(容量% ) く 0.1 く 0.1 18.0 く 0.1 く 0.1 ナフテン分(容量 ¾) く 0.1 <0.1 31.4 く 0.1 53.2∑ / (") 387.6 384.9 364.2 352.7 382.2 Sulfur (mass ppm) <1 <1 5 <1 <1 Aromatic content (volume%) less than 0.1 0.1 8.0 less than 0.1 less than 0.1 naphthene (volume ¾) less than 0.1 < 0.1 31.4 to 0.1 53.2
15°Cにおける密度(kg/m3) 773 780 822 768 805Density at 15 ° C ( kg / m 3 ) 773 780 822 768 805
30°Cにおける動粘度(mm2/s) 2.9 3.7 3.4 2.3 2.8 蒸留性状 10%留出温度 C) 205.0 248.5 215.5 183.5 190.5 Kinematic viscosity at 30 ° C (mm 2 / s) 2.9 3.7 3.4 2.3 2.8 Distillation properties 10% distillation temperature C) 205.0 248.5 215.5 183.5 190.5
50%留出温度 C) 263.0 2フ7.5 266.0 248.5 251.5 50% distillation temperature C) 263.0 2 F 7.5 266.0 248.5 251.5
90%留出温度 C) 309.0 314.5 325.0 314.0 316.090% distillation temperature C) 309.0 314.5 325.0 314.0 316.0
E 250 ( ¾ ) 37.6 17.1 33.9 50.9 46.4 セタン価 81 85 63 74 64 セタン指数 84.5 89.4 58.3 79.8 60.8 流動点 (°c) -5.0 - 5.0 -10.0 - 5.0 -10.0 目詰まり点 ΓΟ -5.0 -2.0 -6.0 -4.0 -8.0 徐冷曇り点 C) -4.0 0.0 -4.0 -3.0 -6.0 着火性試験 86 84 106 92 100 高温始動性試験 A A B B B ゴム膨潤試験 A A A C B 燃費試験 97 95 100 105 94 E 250 (¾) 37.6 17.1 33.9 50.9 46.4 Cetane number 81 85 63 74 64 Cetane index 84.5 89.4 58.3 79.8 60.8 Pour point (° c) -5.0-5.0 -10.0-5.0 -10.0 Clogging point ΓΟ -5.0 -2.0 -6.0 -4.0 -8.0 Slow cooling cloud point C) -4.0 0.0 -4.0 -3.0 -6.0 Ignition test 86 84 106 92 100 High temperature startability test AABBB Rubber swelling test AAACB Fuel consumption test 97 95 100 105 94

Claims

請求の範囲 The scope of the claims
[1] 炭素数 10〜24のパラフィンの組成が下記式(1— 1)で表される条件を満たし、 徐冷曇り点が 6. 0°C以下であり、かつ、  [1] The composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-1), the slow-cooling cloud point is 6.0 ° C or less, and
流動点が 7. 5°C以下である  The pour point is 7.5 ° C or less.
ことを特徴とする軽油組成物。  A gas oil composition characterized by that.
[数 1]  [Number 1]
24  twenty four
340.0 < Y f(n) < 400.0 (1 - 1)  340.0 <Y f (n) <400.0 (1-1)
[式(1— 1)中、 nはパラフィンの炭素数を示し、 f (n)は下記式(2): [In the formula (1-1), n represents the carbon number of paraffin, and f (n) represents the following formula (2):
[数 2] f(n) = 27.45 - 3.55(0 / a) - 0.65(c I a) (2)  [Equation 2] f (n) = 27.45-3.55 (0 / a)-0.65 (c I a) (2)
(nは 10〜24の整数を示し、 a、 b及び cはそれぞれ炭素数 nのパラフィンの全量に占 める炭素数 nのノルマルパラフィン、炭素数 nの 1分岐のイソパラフィン及び炭素数 n の 2分岐以上のイソパラフィンの割合 (モル換算値)を示す。 ) (n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
で表される炭素数 nのパラフィン組成パラメータを示す。 ]  The paraffin composition parameter of carbon number n represented by these is shown. ]
[2] セタン価が 65以上であり、硫黄含有量が 10質量 ppm以下であり、芳香族分の含有 量が 1質量%以下であり、ナフテン分の含有量が 5質量%以下であり、目詰まり点が 5°C以下であることを特徴とする、請求項 1に記載の軽油組成物。 [2] The cetane number is 65 or more, the sulfur content is 10 mass ppm or less, the aromatic content is 1 mass% or less, the naphthene content is 5 mass% or less, The gas oil composition according to claim 1, wherein the clogging point is 5 ° C or less.
[3] 炭素数 10〜24のパラフィンの組成が下記式(1— 2)で表される条件を満たし、 留出温度 250°Cにおける留出量 E250が 5〜45%であり、かつ、 [3] The composition of the paraffin having 10 to 24 carbon atoms satisfies the condition represented by the following formula (1-2), the distillation amount E250 at a distillation temperature of 250 ° C is 5 to 45%, and
徐冷曇り点が 6. 0°Cを超える  Slow cooling cloud point exceeds 6.0 ° C
ことを特徴とする軽油組成物。  A gas oil composition characterized by that.
[数 3]  [Equation 3]
24  twenty four
370.0 f(")≤ 430.0 (1 - 2)  370.0 f (") ≤ 430.0 (1-2)
[式(1— 2)中、 nはパラフィンの炭素数を示し、 f (n)は下記式(2): [In the formula (1-2), n represents the carbon number of paraffin, and f (n) represents the following formula (2):
画 f(n) = 27.45 - 3.55(0 / α) - 0.65(c / a) (2) (nは 10〜24の整数を示し、 a、 b及び cはそれぞれ炭素数 nのパラフィンの全量に占 める炭素数 nのノルマルパラフィン、炭素数 nの 1分岐のイソパラフィン及び炭素数 n の 2分岐以上のイソパラフィンの割合 (モル換算値)を示す。 ) F (n) = 27.45-3.55 (0 / α)-0.65 (c / a) (2) (n represents an integer of 10 to 24, and a, b, and c are n-paraffins, n-branched isoparaffins, and n-2 Indicates the ratio of isoparaffins that are branched or higher (in terms of mole).
で表される炭素数 nのパラフィン組成パラメータを示す。 ] The paraffin composition parameter of carbon number n represented by these is shown. ]
セタン価が 65以上であり、硫黄含有量が 10質量 ppm以下であり、芳香族分の含有 量が 1質量%以下であり、ナフテン分の含有量が 5質量%以下であり、目詰まり点が 5°C以下であることを特徴とする、請求項 3に記載の軽油組成物。  The cetane number is 65 or more, the sulfur content is 10 mass ppm or less, the aromatic content is 1 mass% or less, the naphthene content is 5 mass% or less, and the clogging point is The gas oil composition according to claim 3, wherein the temperature is 5 ° C or lower.
PCT/JP2007/054455 2006-03-31 2007-03-07 Light oil compositions WO2007113977A1 (en)

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